3-heterocyclyl-substituted benzoyl derivatives

ABSTRACT

Benzoyl derivatives of the formula I 
                         
where the variables have the following meanings:
     R 1 , R 2  are hydrogen, nitro, halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl or C 1 –C 6 -haloalkylsulfonyl;   R 3  is hydrogen, halogen or alkyl;   R 4 , R 5  are hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio, dialkylamino, phenyl or carbonyl, it being possible for the 6 last-mentioned radicals to be substituted;   X is O, S, NR 9 , CO or CR 10 R 11 ;   Y is O, S, NR 12 , CO or CR 13 R 14 ;   R 15  is pyrazole which is unsubstituted or substituted, linked in the 4-position and has attached to it in the 5-position a hydroxyl or sulfonyloxy radical;
 
and the agriculturally useful salts thereof; processes and intermediates for the preparation of the 3-heterocyclyl-substituted benzoyl derivatives, compositions comprising them; and the use of these derivatives or compositions comprising them for controlling undesirable plants.

The present invention relates to 3-heterocyclyl-substituted benzoyl derivatives of the formula-I

where the variables have the following meanings:

-   R¹, R² are hydrogen, nitro, halogen, cyano, C₁–C₆-alkyl,     C₁–C₆-haloalkyl, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy, C₁–C₆-alkylthio,     C₁–C₆-haloalkylthio, C₁–C₆-alkylsulfinyl, C₁–C₆-haloalkylsulfinyl,     C₁–C₆-alkylsulfonyl or C₁–C₆-haloalkylsulfonyl; -   R³ is hydrogen, halogen or C₁–C₆-alkyl; -   R⁴, R⁵ are hydrogen, halogen, cyano, nitro, C₁–C₄-alkyl,     C₁–C₄-alkoxy-C₁–C₄-alkyl, di(C₁–C₄-alkoxy)-C₁–C₄-alkyl,     di(C₁–C₄-alkyl)-amino-C₁–C₄-alkyl,     [2,2-di(C₁–C₄-alkyl)-1-hydrazino]-C₁–C₄-alkyl,     C₁–C₆-alkyliminooxy-C₁–C₄-alkyl, C₁–C₄-alkoxycarbonyl-C₁–C₄-alkyl,     C₁–C₄-alkylthio-C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-cyanoalkyl,     C₃–C₈-cycloalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy,     C₁–C₄-haloalkoxy, hydroxyl, C₁–C₄-alkylcarbonyloxy, C₁–C₄-alkylthio,     C₁–C₄-haloalkylthio, di(C₁–C₄-alkyl)amino, COR⁶, phenyl or benzyl,     it being possible for the two last-mentioned substituents to be     fully or partially halogenated and/or to have attached to them one     to three of the following groups:     -   nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or         C₁–C₄-haloalkoxy; or -   R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono-     to tetrasubstituted by C₁–C₄-alkyl and/or which can be interrupted     by oxygen or by a nitrogen which is unsubstituted or substituted by     C₁–C₄-alkyl; or -   R⁴ and R⁵ together with the corresponding carbon form a carbonyl or     thiocarbonyl group; -   R⁶ is hydrogen, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy,     C₁–C₄-alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy, C₃–C₆-alkenyloxy,     C₃–C₆-alkynyloxy or NR⁷R⁸; -   R⁷ is hydrogen or C₁–C₄-alkyl; -   R⁸ is C₁–C₄-alkyl; -   X is O, S, NR⁹, CO or CR¹⁰R¹¹; -   Y is O, S, NR¹², CO or CR¹³R¹⁴; -   R⁹, R¹² are hydrogen or C₁–C₄-alkyl; -   R¹⁰, R¹¹, R¹³, R¹⁴ are hydrogen, C₁–C₄-alkyl, C₁–C₄-haloalkyl,     C₁–C₄-alkoxycarbonyl, C₁–C₄ -haloalkoxycarbonyl or CONR⁷R⁸; or -   R⁴ and R⁹ or R⁴ and R¹⁰ or R⁵ and R¹² or R⁵ and R¹³ together form a     C₂–C₆-alkanediyl chain which can be mono- to tetrasubstituted by     C₁–C₄-alkyl and/or interrupted by oxygen or by a nitrogen which is     unsubstituted or substituted by C₁–C₄-alkyl; -   R¹⁵ is a pyrazole of the formula II which is linked in the     4-position

-   -   where     -   R¹⁶ is C₁–C₆-alkyl;     -   Z is H or SO₂R¹⁷;     -   R¹⁷ is C₁–C₄-alkyl, C₁–C₄-haloalkyl, phenyl or phenyl which is         partially or fully halogenated and/or has attached to it one to         three of the following groups:         -   nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or             C₁–C₄-haloalkoxy;     -   R¹⁸ is hydrogen or C₁–C₆-alkyl;         where X and Y are not simultaneously oxygen or sulfur;

with the exception of 4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1-ethyl-5-hydroxy-1H-pyrazole, 4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]1,3-dimethyl-5-hydroxy-1H-pyrazole, 4-[2-chloro-3-(5-cyano-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole, 4-[2-chloro-3-(4,5-dihydrothiazol-2-yl)-4-methylsulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole and 4-[2-chloro-3-(thiazoline-4,5-dion-2-yl)-4-methylsulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole;

or the agriculturally useful salts thereof.

The invention furthermore relates to processes and intermediates for the preparation of compounds of the formula I, to compositions comprising them, and to the use of these derivatives or compositions comprising them for the control of harmful plants.

Pyrazol-4-yl-benzoyl derivatives have been disclosed in the literature, for example in WO 96/26206.

However, the herbicidal properties of the compounds which have been known to date and their compatibility properties regarding crop plants are only moderately satisfactory.

It is an object of the present invention to provide novel, in particular herbicidally active, compounds which have improved properties.

We have found that this object is achieved by the 3-heterocyclyl-substituted benzoyl derivatives of the formula I and by their herbicidal activity.

We have furthermore found herbicidal compositions which comprise the compounds I and which have a very good herbicidal activity. Moreover, we have found processes for the preparation of these compositions and methods of controlling undesirable vegetation using the compounds I.

Depending on the substitution pattern, the compounds of the formula I can contain one or more chiral centers, in which case they exist as enantiomer or diastereomer mixtures. The present invention relates to the pure enantiomers or diastereomers and to the mixtures thereof.

The compounds of the formula I may also exist in the form of their agriculturally useful salts, the type of salt generally being of no importance. In general, suitable salts are the salts of those cations or the acid addition salts of those acids whose cations, or anions, respectively, do not adversely affect the herbicidal activity of the compounds I.

Suitable cations are, in particular, ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium, it being possible in this case, if desired, for one to four hydrogen atoms to be replaced by C₁–C₄-alkyl, hydroxy-C₁–C₄- alkyl, C₁–C₄-alkoxy-C₁–C₄-alkyl, hydroxy-C₁–C₄-alkoxy-C₁–C₄-alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2-(2-hydroxyeth-1-oxy)eth-1-ylammonium, di(2-hydroxyeth-1-yl)ammonium, trimethylbenzylammonium, in addition phosphonium ions, sulfonium ions, preferably tri(C₁–C₄-alkyl)sulfonium and sulfoxonium ions, preferably tri (C₁–C₄-alkyl) sulfoxonium.

Anions of useful acid addition salts are mainly chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C₁–C₄-alkanoic acids, preferably formate, acetate, propionate and butyrate.

The organic moieties mentioned for the substituents R¹-R¹⁸ or as radicals on phenyl rings are collective terms for individual enumerations of the individual group members. All hydrocarbon chains, ie. all alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkyliminooxy, alkylcarbonyloxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkenyloxy, alkynyloxy, dialkylamino, dialkylhydrazino, alkoxyalkyl, hydroxyalkoxyalkyl, dialkoxyalkyl, alkylthioalkyl, dialkylaminoalkyl, dialkylhydrazinoalkyl, alkyliminooxyalkyl, alkoxycarbonylalkyl and alkoxyalkoxy moieties, can be straight-chain or branched, Unless otherwise specified, halogenated substituents preferably have attached to them one to five identical or different halogen atoms. The meaning of halogen is in each case fluorine, chlorine, bromine or iodine.

Other examples of meanings are:

-   -   C₁–C₄-alkyl and the alkyl moieties of         di-(C₁–C₄-alkoxy)-C₁–C₄-alkyl,         [2,2-di(C₁–C₄-alkyl)-1-hydrazino]-C₁–C₄-alkyl,         C₁–C₆-alkyliminooxy-C₁–C₄-alkyl,         hydroxy-C₁–C₄-alkoxy-C₁–C₄-alkyl and C₁–C₄-alkylcarbonyloxy: for         example methyl, ethyl, propyl, 1-methylethyl, butyl,         1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;     -   C₁–C₆-alkyl: C₁–C₄-alkyl as mentioned above and, for example,         pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,         2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl,         1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,         3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,         1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,         2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,         2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl and         1-ethyl-3-methylpropyl;     -   C₁–C₄-haloalkyl: a C₁–C₄-alkyl radical as mentioned above which         is partially or fully substituted by fluorine, chlorine, bromine         and/or iodine, for example chloromethyl, dichloromethyl,         trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,         chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl,         2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl,         2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,         2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,         2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl,         3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl,         2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl,         2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl,         3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl,         heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl,         1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl,         4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl;     -   C₁–C₆-haloalkyl: C₁–C₄-haloalkyl as mentioned above and, for         example, 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl,         5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl,         6-bromohexyl, 6-iodohexyl and dodecafluorohexyl;     -   C₁–C₄-cyanoalkyl: for example cyanomethyl, 1-cyanoeth-1-yl,         2-cyanoeth-1-yl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl,         3-cyanoprop-1-yl, 1-cyanoprop-2-yl, 2-cyanoprop-2-yl,         1-cyanobut-1-yl, 2-cyanobut-1-yl, 3-cyanobut-1-yl,         4-cyanobut-1-yl, 1-cyanobut-2-yl, 2-cyanobut-2-yl,         1-cyanobut-3-yl, 2-cyanobut-3-yl, 1-cyano-2-methylprop-3-yl,         2-cyano-2-methylprop-3-yl, 3-cyano-2-methylprop-3-yl and         2-cyanomethylprop-2-yl;     -   C₁–C₄-alkoxy and the alkoxy moieties of         di-(C₁–C₄-alkoxy)-C₁–C₄-alkyl and         hydroxy-C₁–C₄-alkoxy-C₁–C₄-alkyl: for example methoxy, ethoxy,         propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy,         2-methylpropoxy and 1,1-dimethylethoxy;     -   C₁–C₆-alkoxy: C₁–C₄-alkoxy as mentioned above and, for example,         pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methoxylbutoxy,         1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy,         1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy,         3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy,         1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy,         2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy,         2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy,         1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy;     -   C₁–C₄-haloalkoxy: a C₁–C₄-alkoxy radical as mentioned above         which is partially or fully substituted by fluorine, chlorine,         bromine and/or iodine, for example fluoromethoxy,         difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy,         bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy,         2-bromomethoxy, 2-iodoethoxy, 2,2-difluoroethoxy,         2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy,         2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,         2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy,         3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy,         2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy,         2,3-difluoropropoxy, 2,3-dichloropropoxy,         3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy,         2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy,         1-(fluoromethyl)-2-fluoroethoxy,         1-(chloromethyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromoethoxy,         4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and         nonafluorobutoxy;     -   C₁–C₆-haloalkoxy: C₁–C₄-haloalkoxy as mentioend above and, for         example, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy,         5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy,         6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy and         dodecafluorohexoxy;     -   C₁–C₆-alkyliminooxy and the C₁–C₆-akyliminooxy moieties of         C₁–C₆-alkyliminooxy-C₁–C₄-alkyl: for example methyliminooxy,         ethyliminooxy, 1-propyliminooxy, 2-propyliminooxy,         1-butyliminooxy, 2-butyliminooxy, 2-methylprop-1-yliminooxy,         1-pentyliminooxy, 2-pentyliminooxy, 3-pentyliminooxy,         3-methylbut-2-yliminoxy, 2-methylbut-1-yliminooxy,         3-methylbut-1-yliminooxy, 1-hexyliminooxy, 2-Hexyliminooxy,         3-hexyliminooxy, 2-methylpent-1-yliminooxy,         3-methylpent-1-yliminooxy, 4-methylpent-1-yliminooxy,         2-ethylbut-1-yliminooxy, 3-ethylbut-1-yliminooxy,         2,3-dimethylbut-1-yliminooxy, 3-methylpent-2-yliminooxy,         4-methylpent-2-yliminooxy and 3,3-dimethylbut-2-yliminooxy;     -   C₁–C₄-alkylthio: for example methylthio, ethylthio, propylthio,         1-methylethylthio, butylthio, 1-methylpropylthio,         2-methylpropylthio and 1,1-dimethylethylthio;     -   C₁–C₆-alkylthio: C₁–C₄-alkylthio as mentioned above and, for         example, pentylthio, 1-methylbutylthio, 2-methylbutylthio,         3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio,         hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio,         1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio,         4-methylpentylthio, 1,1-dimethylbutylthio,         1,2-dimethylbutylthio, 1,3-dimethylbutylthio,         2,2-dimethylbutylthio, 2,3-dimethylbutylthio,         3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio,         1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio,         1-ethyl-1-methylpropylthio and 1-ethyl-2-methylpropylthio;     -   C₁–C₄-haloalkylthio: a C₁–C₄-alkylthio radical as mentioned         above, which is partially or fully substituted by fluorine,         chlorine, bromine and/or iodine, for example fluoromethylthio,         difluoromethylthio, trifluoromethylthio,         chlorodifluoromethylthio, bromodifluoromethylthio,         2-fluorethylthio, 2-chloroethylthio, 2-bromoethylthio,         2-iodoethylthio, 2,2-difluoroethylthio,         2,2,2-trifluoroethylthio, 2,2,2-trichloroethylthio,         2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio,         2,2-dichloro-2-fluoroethylthio, pentafluoroethylthio,         2-fluoropropylthio, 3-fluoropropylthio, 2-chloropropylthio,         3-chloropropylthio, 2-bromopropylthio, 3-bromopropylthio,         2,2-difluoropropylthio, 2,3-difluoropropylthio,         2,3-dichloropropylthio, 3,3,3-trifluoropropylthio,         3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio,         heptafluoropropylthio, 1-(fluoromethyl)-2-fluoroethylthio,         1-(chloromethyl)-2-chloroethylthio,         1-(bromomethyl)-2-bromoethylthio, 4-fluorobutylthio,         4-chlorobutylthio, 4-bromobutylthio and nonafluorobutylthio;     -   C₁–C₆-haloalkylthio: C₁–C₄-haloalkylthio as mentioned above and,         for example, 5-fluoropentylthio, 5-chloropentylthio,         5-bromopentylthio, 5-iodopentylthio, undecafluoropentylthio,         6-fluorohexylthio, 6-chlorohexylthio, 6-bromohexylthio,         6-iodohexylthio and dodecafluorohexylthio;     -   C₁–C₆-alkylsulfinyl (C₁–C₆-alkyl-S(═O)—): for example         methylsulfinyl, ethylsulfinyl, propylsulfinyl,         1-methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl,         2-methylpropylsulfinyl, 1,1-dimethylethylsulfinyl,         pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl,         3-methylbutylsulf inyl, 2,2-dimethylpropylsulfinyl,         1-ethylpropylsulfinyl, 1,1-dimethylpropylsulfinyl,         1,2-dimethylpropylsulfinyl, hexylsulfinyl,         1-methylpentylsulfinyl, 2-methylpentylsulfinyl,         3-methylpentylsulfinyl, 4-methylpentylsulfinyl,         1,1-dimethylbutylsulfinyl, 1,2-dimethylbutylsulfinyl,         1,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl,         2,3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl,         1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl,         1,1,2-trimethylpropylsulfinyl, 1,2,2-trimethylpropylsulfinyl,         1-ethyl-1-methylpropylsulfinyl and         1-ethyl-2-methylpropylsulfinyl;     -   C₁–C₆-haloalkylsulfinyl: a C₁–C₆-alkylsulfinyl radical as         mentioned above which is partially or fully substituted by         fluorine, chlorine, bromine and/or iodine, for example         fluoromethylsulfinyl, difluoromethylsulfinyl,         trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl,         bromodifluoromethylsulfinyl, 2-fluoroethylsulfinyl,         2-chloroethylsulfinyl, 2-bromoethylsulfinyl,         2-iodoethylsulfinyl, 2,2-difluoroethylsulfinyl,         2,2,2-trifluoroethylsulfinyl, 2,2,2-trichloroethylsulfinyl,         2-chloro-2-fluoroethylsulfinyl,         2-chloro-2,2-difluoroethylsulfinyl,         2,2-dichloro-2-fluoroethylsulfinyl, pentafluoroethylsulfinyl,         2-fluoropropylsulfinyl, 3-fluoropropylsulfinyl,         2-chloropropylsulfinyl, 3-chloropropylsulfinyl,         2-bromopropylsulfinyl, 3-bromopropylsulfinyl,         2,2-difluoropropylsulfinyl, 2,3-difluoropropylsulfinyl,         2,3-dichloropropylsulfinyl, 3,3,3-trifluoropropylsulfinyl,         3,3,3-trichloropropylsulfinyl,         2,2,3,3,3-pentafluoropropylsulfinyl, heptafluoropropylsulfinyl,         1-(fluoromethyl)-2-fluoroethylsulfinyl,         1-(chloromethyl)-2-chloroethylsulfinyl,         1-(bromomethyl)-2-bromoethylsulfinyl, 4-fluorobutylsulfinyl,         4-chlorobutylsulfinyl, 4-bromobutylsulfinyl,         nonafluorobutylsulfinyl, 5-fluoropentylsulfinyl,         5-chloropentylsulfinyl, 5-bromopentylsulfinyl,         5-iodopentylsulfinyl, undecafluoropentylsulfinyl,         6-fluorohexylsulfinyl, 6-chlorohexylsulfinyl,         6-bromohexylsulfinyl, 6-iodohexylsulfinyl and         dodecafluorohexylsulfinyl;     -   C₁–C₆-alkylsulfonyl (C₁–C₆-alkyl-S(═O)₂-): for example         methylsulfonyl, ethylsulfonyl, propylsulfonyl,         1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl,         2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl,         pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl,         3-methylbutylsulfonyl, 1,1-dimethylpropylsulfonyl,         1,2-dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl,         1-ethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl,         2-methylpentylsulfonyl, 3-methylpentylsulfonyl,         4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl,         1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl,         2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl,         3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl,         2-ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl,         1,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropylsulfonyl         and 1-ethyl-2-methylpropylsulfonyl;     -   C₁–C₆-haloalkylsulfonyl: a C₁–C₆-alkylsulfonyl radical as         mentioned above which is partially or fully substituted by         fluorine, chlorine, bromine and/or iodine, for example         fluoromethylsulfonyl, difluoromethylsulfonyl,         trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl,         bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2         -chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl,         2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl,         2-chloro-2-fluoroethylsulfonyl,         2-chloro-2,2-difluoroethylsulfonyl,         2,2-dichloro-2-fluoroethylsulfonyl,         2,2,2-trichloroethylsulfonyl, pentafluoroethylsulfonyl,         2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl,         2-chloropropylsulfonyl, 3-chloropropylsulfonyl,         2-bromopropylsulfonyl, 3-bromopropylsulfonyl,         2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl,         2,3-dichloropropylsulfonyl, 3,3,3-trifluoropropylsulfonyl,         3,3,3-trichloropropylsulfonyl,         2,2,3,3,3-pentafluoropropylsulfonyl, heptafluoropropylsulfonyl,         1-(fluoromethyl)-2-fluoroethylsulfonyl,         1-(chloromethyl)-2-chloroethylsulfonyl,         1-(bromomethyl)-2-bromoethylsulfonyl, 4-fluorobutylsulfonyl,         4-chlorobutylsulfonyl, 4-bromobutylsulfonyl,         nonafluorobutylsulfonyl, 5-fluoropentylsulfonyl,         5-chloropentylsulfonyl, 5-bromopentylsulfonyl,         5-iodopentylsulfonyl, 6-fluorohexylsulfonyl,         6-bromohexylsulfonyl, 6-iodohexylsulfonyl and         dodecafluorohexylsulfonyl;     -   C₁–C₄-alkoxycarbonyl: for example methoxycarbonyl,         ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl,         butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl         and 1,1-dimethoxycarbonyl;     -   C₁–C₄-haloalkoxycarbonyl: a C₁–C₄-alkoxycarbonyl as mentioned         above which is partially or fully substituted by fluorine,         chlorine, bromine and/or iodine, for example         fluoromethoxycarbonyl, difluoromethoxycarbonyl,         trifluoromethoxycarbonyl, chlorodifluoromethoxycarbonyl,         bromodifluoromethoxycarbonyl, 2-fluoroethoxycarbonyl,         2-chloroethoxycarbonyl, 2-bromoethoxycarbonyl,         2-iodoethoxycarbonyl, 2,2-difluoroethoxycarbonyl,         2,2,2-trifluoroethoxycarbonyl, 2-chloro-2-fluoroethoxycarbonyl,         2-chloro-2,2-difluoroethoxycarbonyl,         2,2-dichloro-2-fluoroethoxycarbonyl,         2,2,2-trichloroethoxycarbonyl, pentafluoroethoxycarbonyl,         2,2-fluoropropoxycarbonyl, 3-fluoropropoxycarbonyl,         2-chloropropoxycarbonyl, 3-chloropropoxycarbonyl,         2-bromopropoxycarbonyl, 3-bromopropoxycarbonyl,         2,2-difluoropropoxycarbonyl, 2,3-difluoropropoxycarbonyl,         2,3-dichloropropoxycarbonyl, 3,3,3-trifluoropropoxycarbonyl,         3,3,3-trichloropropoxycarbonyl,         2,2,3,3,3-pentafluoropropoxycarbonyl,         heptafluoropropoxycarbonyl,         1-(fluoromethyl)-2-fluoroethoxycarbonyl,         1-(chloromethyl)-2-chloroethoxycarbonyl,         1-(bromomethyl)-2-bromoethoxycarbonyl, 4-fluorobutoxycarbonyl,         4-chlorobutoxycarbonyl, 4-bromobutoxycarbonyl and         4-iodobutoxycarbonyl;     -   C₃–C₆-alkenyloxy: for example prop-1-en-1-yloxy,         prop-2-en-1-yloxy, 1-methylethenyloxy, buten-1-yloxy,         buten-2-yloxy, buten-3-yloxy, 1-methylprop-1-en-1-yloxy,         2-methylprop-1-en-1-yloxy, 1-methylprop-2-en-1-yloxy,         2-methylprop-2-en-1-yloxy, penten-1-yloxy, penten-2-yloxy,         penten-3-yloxy, penten-4-yloxy, 1-methylbut-1-en-1-yloxy,         2-methylbut-1-en-1-yloxy, 3-methylbut-1-en-1-yloxy,         1-methylbut-2-en-1-yloxy, 2-methylbut-2-en-1-yloxy,         3-methylbut-2-en-1-yloxy, 1-methylbut-3-en-1-yloxy,         2-methylbut-3-en-1-yloxy, 3-methylbut-3-en-1-yloxy,         1,1-dimethylprop-2-en-1-yloxy, 1,2-dimethylprop-1-en-1-yloxy,         1,2-dimethylprop-2-en-1-yloxy, 1-ethylprop-1-en-2-yloxy,         1-ethylprop-2-en-1-yloxy, hex-1-en-1-yloxy, hex-2 -en-1-yloxy,         hex-3-en-1-yloxy, hex-4-en-1-yloxy, hex-5-en-1-yloxy,         1-methylpent-1-en-1-yloxy, 2-methylpent-1-en-1-yloxy,         3-methylpent-1-en-1-yloxy, 4-methylpent-1-en-1-yloxy,         1-methylpent-2-en-1-yloxy, 2-methylpent-2-en-1-yloxy,         3-methylpent-2-en-1-yloxy, 4-methylpent-2-en-1-yloxy,         1-methylpent-3-en-1-yloxy, 2-methylpent-3-en-1-yloxy,         3-methylpent-3-en-1-yloxy, 4-methylpent-3-en-1-yloxy,         1-methylpent-4-en-1-yloxy, 2-methylpent-4-en-1-yloxy,         3-methylpent-4-en-1-yloxy, 4-methylpent-4-en-1-yloxy,         1,1-dimethylbut-2-en-1-yloxy, 1,1-dimethylbut-3-en-1-yloxy,         1,2-dimethylbut-1-en-1-yloxy, 1,2-dimethylbut-2-en-1-yloxy,         1,2-dimethylbut-3-en-1-yloxy, 1,3-dimethylbut-1-en-1-yloxy,         1,3-dimethylbut-2-en-1-yloxy, 1,3-dimethylbut-3-en-1-yloxy,         2,2-dimethylbut-3-en-1-yloxy, 2,3-dimethylbut-1-en-1-yloxy,         2,3-dimethylbut-2-en-1-yloxy, 2,3-dimethylbut-3-en-1-yloxy,         3,3-dimethylbut-1-en-1-yloxy, 3,3-dimethylbut-2-en-1-yloxy,         1-ethylbut-1-en-1-yloxy, 1-ethylbut-2-en-1-yloxy,         1-ethylbut-3-en-1-yloxy, 2-ethylbut-1-en-1-yloxy,         2-ethylbut-2-en-1-yloxy, 2-ethylbut-3-en-1-yloxy,         1,1,2-trimethylprop-2-en-1-yloxy,         1-ethyl-1-methylprop-2-en-1-yloxy,         1-ethyl-2-methylprop-2-en-1-yloxy and         1-ethyl-2-methylprop-2-en-1-yloxy;     -   C₃–C₆-alkynyloxy: for example prop-1-yn-1-yloxy,         prop-2-yn-1-yloxy, but-1-yn-1-yloxy, but-1-yn-3-yloxy,         but-1-yn-4-yloxy, but-2-yn-1-yloxy, pent-1-yn-1-yloxy,         pent-1-yn-3-yloxy, pent-1-yn-4-yloxy, pent-1-yn-5-yloxy,         pent-2-yn-1-yloxy, pent-2-yn-4-yloxy, pent-2-yn-5-yloxy,         3-methylbut-1-yn-3-yloxy, 3-methylbut-1-yn-4-yloxy,         hex-1-yn-1-yloxy, hex-1-yn-3-yloxy, hex-1-yn-4-yloxy,         hex-1-yn-5-yloxy, hex-1-yn-6-yloxy, hex-2-yn-1-yloxy,         hex-2-yn-4-yloxy, hex-2-yn-5-yloxy, hex-2-yn-6-yloxy,         hex-3-yn-1-yloxy, hex-3-yn-2-yloxy, 3-methylpent-1-yn-1-yloxy,         3-methylpent-1-yn-3-yloxy, 3-methylpent-1-yn-4-yloxy,         3-methylpent-1-yn-5-yloxy, 4-methylpent-1-yn-1-yloxy,         4-methylpent-2-yn-4-yloxy and 4-methylpent-2-yn-5-yloxy;     -   di(C₁–C₄-alkyl)amino: for example N,N-dimethylamino,         N,N-diethylamino, N,N-dipropylamino, N,N-di(1-methylethyl)amino,         N,N-dibutylamino, N,N-di(1-methylpropyl)amino,         N,N-di(2-methylpropyl)amino, N,N-di(1,1-dimethylethyl)amino,         N-ethyl-N-methylamino, N-methyl-N-propylamino,         N-methyl-N-(1-methylethyl)amino, N-butyl-N-methylamino,         N-methyl-N-(1-methylpropyl)amino,         N-methyl-N-(2-methylpropyl)amino,         N-(1,1-dimethylethyl)-N-methylamino, N-ethyl-N-propylamino,         N-ethyl-N-(1-methylethyl)amino, N-butyl-N-ethylamino,         N-ethyl-N-(1-methylpropyl)amino,         N-ethyl-N-(2-methylpropyl)amino,         N-ethyl-N-(1,1-dimethylethyl)amino,         N-(1-methylethyl)-N-propylamino, N-butyl-N-propylamino,         N-(1-methylpropyl)-N-propylamino,         N-(2-methylpropyl)-N-propylamino,         N-(1,1-dimethylethyl)-N-propylamino,         N-butyl-N-(1-methylethyl)amino,         N-(1-methylethyl)-N-(1-methylpropyl)amino,         N-(1-methylethyl)-N-(2-methylpropyl)amino,         N-(1,1-dimethylethyl)-N-(1-methylethyl)amino,         N-butyl-N-(1-methylpropyl)amino,         N-butyl-N-(2-methylpropyl)amino,         N-butyl-N-(1,1-dimethylethyl)amino,         N-(1-methylpropyl)-N-(2-methylpropyl)amino,         N-(1,1-dimethylethyl)-N-(1-methylpropyl)amino and         N-(1,1-dimethylethyl)-N-(2-methylpropyl)amino;     -   [2,2di(C₁–C₄-alkyl)-1-hydrazino], and the dialkylhydrazino         moieties of [2,2-di(C₁–C₄-alkyl)-1-hydrazino]-C₁–C₄-alkyl: for         example 2,2-dimethylhydrazino-1, 2,2-diethylhydrazino-1,         2,2-dipropylhydrazino-1, 2,2-di(1-methylethyl)-1-hydrazino,         2,2-dibutylhydrazino-1, 2,2-di(1-methylpropyl)-1-hydrazino,         2,2-di(2-methylpropyl)-1-hydrazino,         2,2-di(1,1-dimethylethyl)-1-hydrazino,         2-ethyl-2-methyl-1-hydrazino, 2-methyl-2-propyl-1-hydrazino,         2-methyl-2-(1-methylethyl)-1-hydrazino,         2-butyl-2-methyl-1-hydrazino,         2-methyl-2-(1-methylpropyl)-1-hydrazino,         2-methyl-2-(2-methylpropyl)-1-hydrazino,         2-(1,1-dimethylethyl)-2-methyl-i-hydrazino,         2-ethyl-2-propyl-1-hydrazino,         2-ethyl-2-(1-methylethyl)-1-hydrazino,         2-butyl-2-ethyl-1-hydrazino,         2-ethyl-2-(1-methylpropyl)-1-hydrazino,         2-ethyl-2-(2-methylpropyl)-1-hydrazino,         2-ethyl-2-(1,1-dimethylethyl)-1-hydrazino,         2-(1-methylethyl)-2-propyl-1-hydrazino,         2-butyl-2-propyl-1-hydrazino,         2-(1-methylpropyl)-2-propyl-1-hydrazino,         2-(2-methylpropyl)-2-propyl-1-hydrazino,         2-(1,1-dimethylethyl)-2-propyl-1-hydrazino,         2-butyl-2-(1-methylethyl)-1-hydrazino,         2-(1-methylethyl)-2-(1-methylpropyl)-1-hydrazino,         2-(1-methylethyl)-2-(2-methylpropyl)-1-hydrazino,         2-(1,1-dimethylethyl)-2-(1-methylethyl)-1-hydrazino,         2-butyl-2-(1-methylpropyl)-1-hydrazino,         2-butyl-2-(2-methylpropyl)-1-hydrazino,         2-butyl-2-(1,1-dimethylethyl)-1-hydrazino,         2-(1-methylpropyl)-2-(2-methylpropyl)-1-hydrazino,         2-(1,1-dimethylethyl)-2-(1-methylpropyl)-1-hydrazino and         2-(1,1-dimethylethyl)-2-(2-methylpropyl)-1-hydrazino;     -   di(C₁–C₄-alkyl)amino-C₁–C₄-alkyl: C₁–C₄-alkyl which is         substituted by di(C₁–C₄-alkyl)amino as mentioned above, for         example N,N-dimethylaminomethyl, N,N-diethylaminomethyl,         N,N-dipropylaminomethyl, N,N-di(1-methylethyl)aminomethyl,         N,N-dibutylaminomethyl, N,N-di(1-methylpropyl)aminomethyl,         N,N-di(2-methylpropyl)aminomethyl,         N,N-di(1,1-dimethylethyl)aminomethyl,         N-ethyl-N-methylaminomethyl, N-methyl-N-propylaminomethyl,         N-methyl-N-(1-methylethyl)aminomethyl,         N-butyl-N-methylaminomethyl,         N-methyl-N-(1-methylpropyl)aminomethyl,         N-methyl-N-(2-methylpropyl)aminomethyl,         N-(1,1-dimethylethyl)-N-methylaminomethyl,         N-methyl-N-propylaminometh yl,         N-ethyl-N-(1-methylethyl)aminomethyl,         N-butyl-N-pethylaminomethyl,         N-ethyl-N-(1-methylpropyl)aminomethyl, N-ethyl-N-(2-methylpropyl         aminomethyl, N-ethyl-N-(1,1-dimethylethyl)aminomethyl,         N-(1-methylethyl)-N-propylaminomethyl,         N-butyl-N-propylaminomethyl,         N-(1l-methylpropyl)-N-propylaminomethyl,         N-(2-methylpropyl)-N-propylaminomethyl,         N-(1,1-dimethylethyl)-N-propylaminomethyl,         N-buty-N-(1-methylethyl)aminomethyl,         N-(1-methylethyl)-N-(1-methylpropyl)aminomethyl,         N-(1-methylethyl)-N-(2-methylpropyl)aminomethyl,         N-(1,1-dimethylethyl)-N-p(1-methylethyl)aminomethyl,         N-butyl-N-(1-methylpropyl)aminomethyl, N-butyl-N-(2-methyl         propyl)aminomethyl, N-butyl-N-(1,1-dimethylethyl)aminomethyl,         N-(1-methylpropyl)-N-(2-methylpropyl)aminomethyl,         N-(1,1-dimethylethyl)-N-(1-methylpropyl)aminomethyl,         N-(1,1-dimethylethyl)-N-(2-methylpropyl)aminomethyl,         2-(N,N-dimethylamino)ethyl, 2-(N,N-diethylamino)ethyl,         2-(N,N-dipropylamino)ethyl, 2-[N,N-di(1-methylethyl)amino]ethyl,         2-[N,(N-dibutylamino]methyl,         2-[N,N-di(1-methylpropyl)amino]ethyl, 2-[N,N-di         (2-methylpropyl)amino]ethyl,         2-[N,N-di(1,1-dimethylethyl)amino]ethyl,         2-([N-ethyl-N-methylamino]ethyl,         2-[N-methyl-N-propylamino]ethyl,         2-[N-methyl-N-(1-methylethyl)amino]ethyl,         2-[N-butyl-N-methylamino]ethyl,         2-[N-methyl-N-(1-methylpropyl)amino]ethyl,         2-[N-methyl-N-(2-methylpropyl)amino]ethyl,         2-[N-(1,1-dimethylethyl)-N-methylamino]ethyl,         2-[N-ethyl-N-propylamino]ethyl,         2-[N-ethyl-N-(1-methylethyl)amino]ethyl,         2-[N-butyl-N-ethylamino]ethyl,         2-[N-ethyl-N-(1-methylpropyl)amino]ethyl,         2-[N-ethyl-N-(2-methylpropyl)amino]ethyl,         2-[N-ethyl-N-(1,1-dimethylethylamino]ethyl,         2-[N-(1-methylethyl)-N-propylamino]ethyl,         2-[N-butyl-N-propylamino]ethyl,         2-[N-(1-methylpropyl)-N-propylamino]ethyl,         2-[N-(2-methylpropyl)-N-propylamino]ethyl,         2-[N-(1,1-dimethylethyl)-N-propylamino]ethyl,         2-[N-butyl-N-(1-methylethyl)amino]ethyl,         2-[N-(1-methylethyl)-N-(1-methylpropyl)amino]ethyl,         2-[N-(1-methylethyl)-N-(2-methylpropyl)amino]ethyl,         2-[N-(1,1-dimethylethyl)-N-(1-methylethyl)amino]ethyl,         2-[N-butyl-N-(1-methylpropyl)amino]ethyl,         2-[N-butyl-N-(2-methylpropyl)amino]ethyl,         2-[N-butyl-N-(1,1-dimethylethyl)amino]ethyl,         2-[N-(1-methylpropyl)-N-(2-methylpropyl)amino]ethyl,         2-[N-(1,1-dimethylethyl)-N-(1-methylpropyl)amino]ethyl,         2-[N-(1,1-dimethylethyl)-N-(2-methylpropyl)amino]ethyl,         3-(N,N-dimethylamino)propyl, 3-(N,N-diethylamino)propyl,         4-(N,N-dimethylamino)butyl und 4-(N,N-diethylamino)butyl;     -   C₁–C₄-alkoxy-C₁–C₄-alkyl: C₁–C₄-alkyl which is substituted by         C₁–C₄-alkoxy as mentioned above, for example methoxymethyl,         ethoxymethyl, propoxymethyl, (1-methylethoxy)methyl,         butoxymethyl, (1-methylpropoxy)methyl, (2-methylpropoxy)methyl,         (1,1-dimethylethoxy)methyl, 2-(methoxy) ethyl, 2-(ethoxy) ethyl,         2-(propoxy)ethyl, 2-(1-methylethoxy)ethyl, 2-(butoxy)ethyl,         2-(1-methylpropoxy)ethyl, 2-(2-methylpropoxy)ethyl,         2-(1,1-dimethylethoxy) ethyl, 2-(methoxy)-propyl,         2-(ethoxy)propyl, 2-(propoxy)propyl, 2-(1-methylethoxy)propyl,         2-(butoxy)propyl, 2-(1-methylpropoxy)propyl,         2-(2-methylpropoxy)propyl, 2-(1,1-dimethylethoxy)propyl,         3-(methoxy)propyl, 3-(ethoxy)-propyl, 3-(propoxy)propyl,         3-(1-methylethoxy)propyl, 3-(butoxy)propyl,         3-(1-methylpropoxy)propyl, 3-(2-methylpropoxy)propyl,         3-(1,1-dimethylethoxy)propyl, 2-(methoxy)butyl, 2-(ethoxy)butyl,         2-(propoxy)butyl, 2-(1-methylethoxy)butyl, 2-(butoxy)butyl,         2-(1-methylpropoxy)butyl, 2-(2-methylpropoxy)butyl,         2-(1,1-dimethylethoxy)butyl, 3-(methoxy)butyl, 3-(ethoxy)butyl,         3-(propoxy)butyl, 3-(1-methylethoxy)butyl, 3-(butoxy)butyl,         3-(1-methylpropoxy)butyl, 3-(2-methylpropoxy)butyl,         3-(1,1-dimethylethoxy)butyl, 4-(methoxy)butyl, 4-(ethoxy)butyl,         4-(propoxy)butyl, 4-(1-methylethoxy)butyl, 4-(butoxy)butyl,         4-(1-methylpropoxy)butyl, 4-(2-methylpropoxy)butyl and         4-(1,1-dimethylethoxy)butyl;     -   C₁–C₄-alkylthio-C₁–C₄-alkyl: C₁–C₄-alkyl which is substituted by         C₁–C₄-alkylthio as mentioned above, for example         methylthiomethyl, ethylthiomethyl, propylthiomethyl,         (1-methylethylthio)methyl, butylthiomethyl, (1-methylpropylthio)         methyl, (2-methylpropylthio) methyl,         (1,1-dimethylethylthio)methyl, 2-methylthioethyl,         2-ethylthioethyl, 2-(propylthio)ethyl,         2-(1-methylethylthio)ethyl, 2-(butylthio)ethyl,         2-(1-methylpropylthio) ethyl, 2-(2-methylpropylthio) ethyl,         2-(1,1-dimethylethylthio)ethyl, 2-(methylthio)propyl,         3-(methylthio)propyl, 2-(ethylthio)propyl, 3-(ethylthio)propyl,         3-(propylthio)propyl, 3-(butylthio)propyl, 4-(methylthio)butyl,         4-(ethylthio)butyl, 4-(propylthio)butyl and 4-(butylthio)butyl;     -   C₁–C₄-alkoxycarbonyl-C₁–C₄-alkyl: C₁–C₄-alkyl which is         substituted by C₁–C₄-alkoxycarbonyl as mentioned above, for         example methoxycarbonylmethyl, ethoxycarbonylmethyl,         propoxycarbonylmethyl, (1-methylethoxycarbonyl)methyl,         butoxycarbonylmethyl, (1-methylpropoxycarbonyl)methyl,         (2-methylpropoxycarbonyl)methyl,         (1,1-dimethylethoxycarbonyl)methyl, 2-(methoxycarbonyl)ethyl,         2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyl)ethyl,         2-(1-methylethoxycarbonyl)ethyl, 2-(butoxycarbonyl)ethyl,         2-(1-methylpropoxycarbonyl)ethyl,         2-(2-methylpropoxycarbonyl)ethyl,         2-(1,1-dimethylethoxycarbonyl)ethyl, 2-(methoxycarbonyl)propyl,         2-(ethoxycarbonyl)propyl, 2-(propoxycarbonyl)propyl,         2-(1-methylethoxycarbonyl)propyl, 2-(butoxycarbonyl)propyl,         2-(1-methylpropoxycarbonyl)propyl,         2-(2-methylpropoxycarbonyl)propyl,         2-(1,1-dimethylethoxycarbonyl)propyl, 3-(methoxycarbonyl)propyl,         3-(ethoxycarbonyl)propyl, 3-(propoxycarbonyl)propyl,         3-(5-methylethoxycarbonyl)propyl, 3-(butoxycarbonyl)propyl,         3-(1-methylpropoxycarbonyl)propyl,         3-(2-methylpropoxycarbonyl)propyl,         3-(1,1-dimethylethoxycarbonyl)propyl, 2-(methoxycarbonyl)butyl,         2-(ethoxycarbonyl)butyl, 2-(propoxycarbonyl)butyl,         2-(1-methylethoxycarbonyl)butyl, 2-(butoxycarbonyl)butyl,         2-(1-methylpropoxycarbonyl)butyl,         2-(2-methylpropoxycarbonyl)butyl,         2-(1,1-dimethylethoxycarbonyl)butyl, 3-(methoxycarbonyl)butyl,         3-(ethoxycarbonyl)butyl, 3-(propoxycarbonyl)butyl,         3-(1-methylethoxycarbonyl)butyl, 3-(butoxycarbonyl)butyl,         3-(1-methylpropoxycarbonyl)butyl,         3-(2-methylpropoxycarbonyl)butyl,         3-(1,1-dimethylethoxycarbonyl)butyl, 4-(methoxycarbonyl)butyl,         4-(ethoxycarbonyl)butyl, 4-(propoxycarbonyl)butyl,         4-(1-methylethoxycarbonyl)butyl, 4-(butoxycarbonyl)butyl,         4-(1-methylpropoxy)butoxy, 4-(2-methylpropoxy)butoxy und         4-(1,1-dimethylethoxycarbonyl)butyl;     -   C₁–C₄-alkoxy-C₂–C₄-alkoxy: C₂–C₄-alkoxy which is substituted by         C₁–C₄-alkoxy as mentioned above, for example 2-(methoxy)ethoxy,         2-(ethoxy)ethoxy, 2-(propoxy)ethoxy, 2-(1-methylethoxy)ethoxy,         2-(butoxy)ethoxy, 2-(1-methylpropoxy)ethoxy,         2-(2-methylpropoxy)ethoxy, 2-(1,1-dimethylethoxy)ethoxy,         2-(methoxy)propoxy, 2-(ethoxy)propoxy, 2-(propoxy)propoxy,         2-(1-methylethoxy)propoxy, 2-(butoxy)propoxy,         2-(1-methylpropoxy)propoxy, 2-(2-methylpropoxy)propoxy,         2-(1,1-dimethylethoxy)propoxy, 3-(methoxy)propoxy,         3-(ethoxy)propoxy, 3-(propoxy)propoxy,         3-(1-methylethoxy)propoxy, 3-(butoxy)propoxy,         3-(1-methylpropoxy)propoxy, 3-(2-methylpropoxy)propoxy,         3-(1,1-dimethylethoxy)propoxy, 2-(methoxy)butoxy,         2-(ethoxy)butoxy, 2-(propoxy)butoxy, 2-(1-methylethoxy)butoxy,         2-(butoxy)butoxy, 2-(1-methylpropoxy)butoxy,         2-(2-methylpropoxy)butoxy, 2-(1,1-dimethylethoxy)butoxy,         3-(methoxy)butoxy, 3-(ethoxy)butoxy, 3-(propoxy)butoxy,         3-(1-methylethoxy)butoxy, 3-(butoxy)butoxy,         3-(1-methylpropoxy)butoxy, 3-(2-methylpropoxy)butoxy,         3-(1,1-dimethylethoxy)butoxy, 4-(methoxy)butoxy,         4-(ethoxy)butoxy, 4-(propoxy)butoxy, 4-(1-methylethoxy)butoxy,         4-(butoxy)butoxy, 4-(1-methylpropoxy)butoxy,         4-(2-methylpropoxy)butoxy and 4-(1,1-dimethylethoxy)butoxy;     -   C₂–C₆-alkanediyl: for example ethane-1,2-diyl, propane-1,3-diyl,         butane-1,4-diyl, pentane-1,5-diyl and hexane-1,6-diyl;     -   C₃–C₈-cycloalkyl: for example cyclopropyl, cyclobutyl,         cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl;

All phenyl rings are preferably unsubstituted or have attached to them one to three halogen atoms and/or a nitro group, a cyano radical and/or one or two methyl, trifluoromethyl, methoxy or trifluoromethoxy substituents.

Preference is given to the 3-heterocyclyl-substituted benzoyl derivatives of the formula I where the variables have the following meanings:

-   R¹, R² are hydrogen, nitro, halogen, cyano, C₁–C₆-alkyl,     C₁–C₆-haloalkyl, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy, C₁–C₆-alkylthio,     C₁–C₆-haloalkylthio, C₁–C₆-alkylsulfinyl, C₁–C₆-haloalkylsulfinyl,     C₁–C₆-alkylsulfonyl or C₁–C₆-haloalkylsulfonyl; -   R³ is hydrogen, halogen or C₁–C₆-alkyl; -   R⁴, R⁵ are hydrogen, halogen, cyano, nitro, C₁–C₄-alkyl,     C₁–C₄-alkoxy-C₁–C₄-alkyl, di(C₁–C₄-alkoxy)-C₁–C₄-alkyl,     di(C₁–C₄-alkyl)-amino-C₁–C₄-alkyl,     [2,2-di(C₁–C₄-alkyl)-1-hydrazino]-C₁–C₄-alkyl,     C₁–C₆-alkyliminooxy-C₁–C₄-alkyl, C₁–C₄-alkoxycarbonyl-C₁–C₄-alkyl,     C₁–C₄-alkylthio-C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-cyanoalkyl,     C₃–C₈-cycloalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy,     C₁–C₄-haloalkoxy, C₁–C₄-alkylthio, C₁–C₄-haloalkylthio,     di(C₁–C₄-alkyl)amino, COR⁶, phenyl or benzyl, it being possible for     the two last-mentioned substituents to be fully or partially     halogenated and/or to have attached to them one to three of the     following groups:     -   nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or         C₁–C₄ -haloalkoxy; -   R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono-     to tetrasubstituted by C₁–C₄-alkyl and/or which can be interrupted     by oxygen or by a nitrogen which is unsubstituted or substituted by     C₁–C₄-alkyl; -   R⁴ and R⁵ together with the corresponding carbon form a carbonyl or     thiocarbonyl group; -   R⁶ is C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy,     C₁–C₄-alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy, C₃–C₆-alkenyloxy,     C₃–C₆-alkynyloxy or NR⁷R⁸; -   R⁷ is hydrogen or C₁–C₄-alkyl; -   R⁸ is C₁–C₄-alkyl; -   X is O, S, NR⁹, CO or CR¹⁰R¹¹; -   Y is O, S, NR¹², CO or CR¹³R¹⁴; -   R⁹, R¹² are hydrogen or C₁–C₄-alkyl; -   R¹⁰, R¹¹, R¹³, R¹⁴ are hydrogen, C₁–C₄-alkyl, C₁–C₄-haloalkyl,     C₁–C₄-alkoxycarbonyl, C₁–C₄-haloalkoxycarbonyl or CONR⁷R⁸; or -   R⁴ and R⁹ or R⁴ and R¹⁰ or R⁵ and R¹² or R⁵ and R¹³ together form a     C₂–C₆-alkanediyl chain which can be mono- to tetrasubstituted by     C₁–C₄-alkyl and/or interrupted by oxygen or by a nitrogen which is     unsubstituted or substituted by C₁–C₄-alkyl; -   R¹⁵ is a pyrazole of the formula II which is linked in the     4-position

-   -   where     -   R¹⁶ is C₁–C₆-alkyl;     -   Z is H or SO₂R¹⁷;     -   R¹⁷ is C₁–C₄-alkyl, C₁–C₄-haloalkyl, phenyl or phenyl which is         partially or fully halogenated and/or has attached to it one to         three of the following groups:         -   nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or             C₁–C₄-haloalkoxy;     -   R¹⁸ is hydrogen or C₁–C₆-alkyl;         where X and Y are not simultaneously oxygen or sulfur;

with the exception of 4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1-ethyl-5-hydroxy-1H-pyrazole, 4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole, 4-[2-chloro-3-(5-cyano-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole, 4-[2-chloro-3-(4,5-dihydrothiazol-2-yl)-4-methylsulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole and 4-[2-chloro-3-(thiazoline-4,5-dion-2-yl)-4-methylsulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole;

or the agriculturally useful salts thereof.

With a view to the use of the compounds of the formula I according to the invention as herbicides, the variables preferably have the following meanings, in each case alone or in combination:

-   R¹, R² are nitro, halogen, cyano, C₁–C₆-alkyl, C₁–C₆-haloalkyl,     C₁–C₆-alkoxy, C₁–C₆-haloalkoxy, C₁–C₆-alkylthio,     C₁–C₆-haloalkylthio, C₁–C₆-alkylsulfinyl, C₁–C₆-haloalkylsulfinyl,     C₁–C₆-alkylsulfonyl or C₁–C₆-haloalkylsulfonyl; especially     preferably nitro, halogen such as, for example, chlorine and     bromine, C₁–C₆-alkyl such as, for example, methyl and ethyl,     C₁–C₆-alkoxy such as, for example, methoxy and ethoxy,     C₁–C₆-haloalkyl such as, for example, difluoromethyl and     trifluoromethyl, C₁–C₆-alkylthio such as, for example, methylthio     and ethylthio, C₁–C₆-alkylsulfinyl such as, for example,     methylsulfinyl and ethylsulfinyl, C₁–C₆-alkylsulfonyl such as, for     example, methylsulfonyl, ethylsulfonyl and propylsulfonyl or     C₁–C₆-haloalkylsulfonyl such as, for example,     trifluoromethylsulfonyl and pentafluoroethylsulfonyl; -   R³ is hydrogen; -   R⁴, R⁵ are hydrogen, halogen, cyano, nitro, C₁–C₄-alkyl,     C₁–C₄-alkoxy-C₁–C₄-alkyl, di(C₁–C₄-alkoxy)-C₁–C₄-alkyl,     di(C₁–C₄-alkyl)amino-C₁–C₄-alkyl,     [2,2-di(C₁–C₄-alkyl)hydrazino-1]-C₁–C₄-alkyl,     C₁–C₆-alkyliminooxy-C₁–C₄-alkyl, C₁–C₄-alkoxycarbonyl-C₁–C₄-alkyl,     C₁–C₄-alkylthio-C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-cyanoalkyl,     C₃–C₈-cycloalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy,     C₁–C₄-haloalkoxy, C₁–C₄-alkylthio, C₁–C₄-haloalkylthio,     di(C₁–C₄-alkyl)amino, COR⁶, phenyl or benzyl, it being possible for     the two last-mentioned substituents to be partially or fully     halogenated and/or to have attached to them one to three of the     following groups:     -   nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or         C₁–C₄-haloalkoxy; or -   R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono-     to tetrasubstituted by C₁–C₄-alkyl and/or which can be interrupted     by oxygen or by a nitrogen which is unsubstituted or substituted by     C₁–C₄-alkyl;     -   R⁴ is especially preferably hydrogen, C₁–C₄-alkyl,         C₁–C₄-haloalkyl, C₁–C₄-alkoxycarbonyl or CONR⁷R⁸;     -   R⁵ is especially preferably hydrogen or C₁–C₄-alkyl; or     -   R⁴ and R⁵ especially preferably form a C₂–C₆-alkanediyl chain         which can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or         which can be interrupted by oxygen or by a nitrogen which is         unsubstituted or substituted by C₁–C₄-alkyl; -   R⁶ is C₁–C₄-alkyl, C₁–C₄-alkoxy or NR⁷R⁸; -   R⁷ is hydrogen or C₁–C₄-alkyl; -   R⁸ is C₁–C₄-alkyl; -   X is O, S, NR⁹, CO or CR¹⁰R¹¹; -   Y is O, S, NR¹² or CR¹³R¹⁴; -   R⁹, R¹² are hydrogen or C₁–C₄-alkyl; -   R¹⁰, R¹¹, R¹³, R¹⁴ are hydrogen, C₁–C₄-alkyl, C₁–C₄-haloalkyl,     C₁–C₄-alkoxycarbonyl, C₁–C₄-haloalkoxycarbonyl or CONR⁷R⁸; or -   R⁴ and R⁹ or R⁴ and R¹⁰ or R⁵ and R¹² or R⁵ and R¹³ together form a     C₂–C₆-alkanediyl chain which can be mono- to tetrasubstituted by     C₁–C₄-alkyl and/or which can be interrupted by oxygen or by a     nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl; -   R¹⁶ is C₁–C₆-alkyl; especially preferably methyl, ethyl, propyl,     2-methylpropyl or butyl; -   Z is H or SO₂R¹⁷; -   R¹⁷ is C₁–C₄-alkyl, phenyl or phenyl which is partially or fully     halogenated and/or has attached to it one to three of the following     groups:     -   nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or         C₁–C₄-haloalkoxy; -   R¹⁸ is hydrogen or C₁–C₆-alkyl; especially preferably hydrogen or     methyl.

The following embodiments of the 3-heterocyclyl-substituted benzoyl derivatives of the formula I must be emphasized:

-   1. In a preferred embodiment of the 3-heterocyclyl-substituted     benzoyl derivatives of the formula I, Z is SO₂R¹⁷.     -   Especially preferred are the 3-heterocyclyl-substituted benzoyl         derivatives of the formula I, where R¹⁸ is hydrogen.     -   Also especially preferred are 3-heterocyclyl-substituted benzoyl         derivatives of the formula I, where R¹⁸ is methyl.         -   Particularly preferred are 3-heterocylyl-substituted benzoyl             derivatives of the formula I, where R¹⁷ is C₁–C₄-alkyl. -   2. In a further preferred embodiment of the     3-heterocyclyl-substituted benzoyl derivatives of the formula I, Z     is hydrogen.     -   Especially preferred are 3-heterocyclyl-substituted benzoyl         derivatives of the formula I where X is oxygen and Y is CR¹³R¹⁴.         -   Particularly preferred are 3-heterocyclyl-substituted             benzoyl derivatives of the formula I where             -   R⁴ is halogen, nitro, C₁–C₄-alkyl,                 C₁–C₄-alkoxy-C₁–C₄-alkyl,                 C₁–C₄-alkoxycarbonyl-C₁–C₄-alkyl,                 C₁–C₄-alkylthio-C₁–C₄-alkyl, C₁–C₄-haloalkyl,                 C₁–C₄-cyanoalkyl, C₃–C₈-cycloalkyl, C₁–C₄-alkoxy,                 C₁–C₄-Alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy,                 C₁–C₄-alkylthio, C₁–C₄-haloalkylthio,                 di(C₁–C₄-alkyl)amino, COR⁶, phenyl or benzyl, it being                 possible for the two last-mentioned substituents to be                 partially or fully halogenated and/or to have attached                 to them one to three of the following groups:                 -   nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl,                     C₁–C₄-alkoxy or C₁–C₄-haloalkoxy;             -   R⁵ is hydrogen or C₁–C₄-alkyl; or             -   R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which                 can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or                 which can be interrupted by oxygen or by a nitrogen                 which is unsubstituted or substituted by C₁–C₄-alkyl; or             -   R⁵ and R¹³ together form a C₂–C₆-alkanediyl chain which                 can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or                 which can be interrupted by oxygen or by a nitrogen                 which is unsubstituted or substituted by C₁–C₄-alkyl.             -   Extraordinarily preferred are 3-heterocyclyl-substituted                 benzoyl derivatives of the formula I where             -   R⁴ is C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxycarbonyl                 or CONR⁷R⁸;             -   R⁵ is hydrogen or C₁–C₄-alkyl; or             -   R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which                 can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or                 which can be interrupted by oxygen or by a nitrogen                 which is unsubstituted or substituted by C₁–C₄-alkyl; or             -   R⁵ and R¹³ together form a C₂–C₆-alkanediyl chain which                 can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or                 which can be interrupted by oxygen or by a nitrogen                 which is unsubstituted or substituted by C₁–C₄-alkyl.             -   Especially extraordinarily preferred are                 3-heterocyclyl-substituted benzoyl derivatives of the                 formula I where R¹⁸ is hydrogen.         -   Also particularly preferred are 3-heterocyclyl-substituted             benzoyl derivatives of the formula I where R⁴ and R⁵ are             hydrogen.             -   Extraordinarily preferred are 3-heterocyclyl-substituted                 benzoyl derivatives of the formula I where R¹⁸ is                 hydrogen.                 -   Especially extraordinarily preferred are                     3-heterocyclyl-substituted benzoyl derivatives of                     the formula I where                 -   R¹ is nitro, C₁–C₆-alkyl such as, for example,                     methyl and ethyl, C₁–C₆-alkoxy such as, for example,                     methoxy and ethoxy, C₁–C₆-haloalkyl such as, for                     example, difluoromethyl and trifluoromethyl,                     C₁–C₆-alkylsulfonyl such as, for example,                     methylsulfonyl, ethylsulfonyl and propylsulfonyl, or                     C₁–C₆-haloalkylsulfonyl such as, for example,                     trifluoromethylsulfonyl and                     pentafluoroethylsulfonyl;                 -   Also especially extraordinarily preferred are                     3-heterocyclyl-substituted benzoyl derivatives of                     the formula I where                 -   R² is nitro, halogen such as, for example, chlorine                     and bromine, C₁–C₆-alkyl such as, for example,                     methyl and ethyl, C₁–C₆-haloalkyl such as, for                     example, difluoromethyl and trifluoromethyl,                     C₁–C₆-alkylthio such as, for example, methylthio and                     ethylthio, C₁–C₆-alkylsulfinyl such as, for example,                     methylsulfinyl and ethylsulfinyl,                     C₁–C₆-alkylsulfonyl such as, for example,                     methylsulfonyl, ethylsulfonyl and propylsulfonyl, or                     C₁–C₆-haloalkylsulfonyl such as, for example,                     trifluoromethylsulfonyl and                     pentafluoroethylsulfonyl.                 -   Also especially extraordinarily preferred is                     4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1-methyl-5-hydroxy-1H-pyrazole.                 -   Also especially extraordinarily preferred are the                     agriculturally useful salts of                     4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1-methyl-5-hydroxy-1H-pyrazole,                     in particular the alkali metal salts, such as, for                     example, lithium, sodium and potassium, and the                     ammonium salts, it being possible in this case, if                     desired, for one to four hydrogen atoms to be                     replaced by C₁–C₄-alkyl, hydroxy-C₁–C₄-alkyl,                     C₁–C₄-alkoxy-C₁–C₄-alkyl,                     hydroxy-C₁–C₄-alkoxy-C₁–C₄-alkyl, phenyl or benzyl,                     preferably ammonium, dimethylammonium,                     diisopropylammonium, tetramethylammonium,                     tetrabutylammonium,                     2-(2-hydroxyeth-1-oxy)eth-1-ylammonium,                     di(2-hydroxyeth-1-yl)ammonium,                     trimethylbenzylammonium.             -   Also extraordinarily preferred are                 3-heterocyclyl-substituted benzoyl derivatives of the                 formula I where R¹⁸ is methyl.                 -   Especially extraordinarily preferred are                     3-heterocyclyl-substituted benzoyl derivatives of                     the formula I where                 -   R¹ is nitro, C₁–C₆-alkyl such as, for example,                     methyl and ethyl, C₁–C₆-alkoxy such as, for example,                     methoxy and ethoxy, C₁–C₆-haloalkyl such as, for                     example, difluoromethyl and trifluoromethyl,                     C₁–C₆-alkylsulfonyl such as, for example,                     methylsulfonyl, ethylsulfonyl and propylsulfonyl, or                     C₁–C₆-haloalkylsulfonyl, for example                     trifluoromethylsulfonyl and                     pentafluoroethylsulfonyl.                 -   Also especially extraordinarily preferred are                     3-heterocyclyl-substituted benzoyl derivatives of                     the formula I where                 -   R² is nitro, halogen such as, for example, chlorine                     and bromine, C₁–C₆-alkyl such as, for example,                     methyl and ethyl, C₁–C₆-haloalkyl such as, for                     example, difluoromethyl and trifluoromethyl,                     C₁–C₆-alkylthio such as, for example, methylthio and                     ethylthio, C₁–C₆-alkylsulfinyl such as, for example,                     methylsulfinyl and ethylsulfinyl,                     C₁–C₆-alkylsulfonyl such as, for example,                     methylsulfonyl, ethylsulfonyl and propylsulfonyl, or                     C₁–C₆-haloalkylsulfonyl such as, for example,                     trifluoromethylsulfonyl and                     pentafluoroethylsulfonyl. -   Also especially preferred are 3-heterocyclyl-substituted benzoyl     derivatives of the formula I where     -   X is S, NR⁹, CO or CR¹⁰R¹¹; or     -   Y is O, S, NR¹² or CO.     -   Particularly preferred are 3-heterocyclyl-substituted benzoyl         derivatives of the formula I where R¹⁸ is hydrogen.     -   Also particularly preferred are 3-heterocyclyl-substituted         benzoyl derivatives of the formula I where R¹⁸ is C₁–C₆-alkyl.         -   Extraordinarily preferred are 3-heterocyclyl-substituted             benzoyl derivatives of the formula I where             -   R⁴ is halogen, cyano, nitro, C₁–C₄-alkyl,                 C₁–C₄-alkoxy-C₁–C₄-alkyl, C₁–C₄ -alkoxycarbonyl-C₁–C₄                 -alkyl, C₁–C₄-alkylthio-C₁–C₄-alkyl, C₁–C₄-haloalkyl,                 C₁ - C₄ - cyanoalkyl, C₃–C₈-cycloalkyl, C₁–C₆-alkoxy,                 C₁–C₄-alkoxy-C₁–C₄-alkoxy, C₁–C₄-haloalkoxy,                 C₁–C₄-alkylthio, C₁–C₄-haloalkylthio,                 di(C₁–C₄-alkyl)amino, COR⁶, phenyl or benzyl, it being                 possible for the two last-mentioned substituents to be                 partially or fully halogenated and/or to have attached                 to them one to three of the following groups:                 -   nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl,                     C₁–C₄-alkoxy or C₁–C₄-haloalkoxy;             -   R⁵ is hydrogen or C₁–C₄-alkyl; or             -   R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which                 can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or                 which can be interrupted by oxygen or by a nitrogen                 which is unsubstituted or substituted by C₁–C₄-alkyl; or             -   R⁴ and R⁹ or R⁴ and R¹⁰ or R⁵ and R¹² or R⁵ and R¹³                 together form a C₂–C₆-alkanediyl chain which can be                 mono- to tetrasubstituted by C₁–C₄-alkyl and/or which                 can be interrupted by oxygen or by a nitrogen which is                 unsubstituted or substituted by C₁–C₄-alkyl.     -   Also particularly preferred are 3-heterocyclyl-substituted         benzoyl derivatives of the formula I where         -   X is S, NR⁹ or CO or         -   Y is O, NR¹² or CO.         -   Extraordinarily preferred are 3-heterocyclyl-substituted             benzoyl derivatives of the formula I where             -   R⁴ is halogen, cyano, nitro, C₁–C₄-alkyl,                 C₁–C₄-alkoxy-C₁–C₄-alkyl,                 C₁–C₄-alkoxycarbonyl-C₁–C₄-alkyl,                 C₁–C₄-alkylthio-C₁–C₄-alkyl, C₁–C₄-haloalkyl,                 C₁–C₄-cyanoalkyl, C₃–C₈-cycloalkyl, C₁–C₆-alkoxy,                 C₁–C₄-alkoxy-C₁–C₄-alkoxy, C₁–C₄-haloalkoxy,                 C₁–C₄-alkylthio, C₁–C₄-haloalkylthio,                 di(C₁–C₄-alkyl)amino, COR⁶, phenyl or benzyl, it being                 possible for the two last-mentioned substituents to be                 partially or fully halogenated and/or to have attached                 to them one to three of the following groups:                 -   nitro, cyano, C₁–C₄-Alkyl, C₁–C₄-haloalkyl,                     C₁–C₄-alkoxy or C₁–C₄-haloalkoxy;             -   R⁵ is hydrogen or C₁–C₄-alkyl; or             -   R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which                 can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or                 which can be interrupted by oxygen or by a nitrogen                 which is unsubstituted or substituted by C₁–C₄-alkyl; or             -   R⁴ and R⁹ or R⁴ and R¹⁰ or R⁵ and R¹² or R⁵ and R¹³                 together form a C₂–C₆-alkanediyl chain which can be                 mono- to tetrasubstituted by C₁–C₄-alkyl and/or which                 can be interrupted by oxygen or by a nitrogen which is                 unsubstituted or substituted by C₁–C₄-alkyl.

Particularly extraordinarily preferred are the compounds Ia1 ({circumflex over (=)}I where R¹=Cl, R²=SO₂CH₃, R³=H, R¹⁶, R¹⁸=CH₃, Z=H), in particular the compounds of Table 1.

TABLE 1 Ia1

No. X R⁴ R⁵ Y Ia1.1 CH₂ H CH₃ O Ia1.2 CH₂ H H O Ia1.3 C(CH₃)₂ H H O Ia1.4 CH₂ H C₂H₅ O Ia1.5 CH₂ CH₃ CH₃ O Ia1.6 CH(CH₃) H CH₃ O Ia1.7 CH(C₂H₅) H CH₃ O Ia1.8 CH[CH(CH₃)₂] H H O Ia1.9 CH₂ H CH(CH₃)₂ O Ia1.10 CH(C₂H₅) H C₂H₅ O Ia1.11 —CH—(CH₂)₄— H O Ia1.12 C═O CH₃ CH₃ O Ia1.13 C═O H C₂H₅ O Ia1.14 C═O C₂H₅ C₂H₅ O Ia1.15 C═O H H O Ia1.16 C═O H CH₃ O Ia1.17 CH₂ H CH₃ S Ia1.18 C(CH₃)₂ H H S Ia1.19 CH₂ H C₂H₅ S Ia1.20 CH₂ CH₃ CH₃ S Ia1.21 CH(CH₃) H CH₃ S Ia1.22 CH(C₂H₅) H CH₃ S Ia1.23 CH(C₂H₅) H C₂H₅ S Ia1.24 —CH—(CH₂)₄— H S Ia1.25 CH[CH(CH₃)₂] H H S Ia1.26 CH₂ H CH(CH₃)₂ S Ia1.27 CH₂ H CH₃ NH Ia1.28 CH₂ H H NH Ia1.29 C(CH₃)₂ H H NH Ia1.30 CH₂ H C₂H₅ NH Ia1.31 CH₂ CH₃ CH₃ NH Ia1.32 CH(CH₃) H CH₃ NH Ia1.33 CH(C₂H₅) H CH₃ NH Ia1.34 CH(C₂H₅) H C₂H₅ NH Ia1.35 —CH—(CH₂4— H NH Ia1.36 CH[CH(CH₃)₂] H H NH Ia1.37 CH₂ H CH(CH₃)₂ NH Ia1.38 CH₂ H CH₃ NCH₃ Ia1.39 CH₂ H H NCH₃ Ia1.40 C(CH₃)₂ H H NCH₃ Ia1.41 CH₂ H C₂H₅ NCH₃ Ia1.42 CH₂ CH₃ CH₃ NCH₃ Ia1.43 CH(CH₃) H CH₃ NCH₃ Ia1.44 CH(C₂H₅) H CH₃ NCH₃ Ia1.45 CH[CH(CH₃)₂] H H NCH₃ Ia1.46 CH₂ H CH(CH₃)₂ NCH₃ Ia1.47 CH(C₂H₅) H C₂H₅ NCH₃ Ia1.48 —CH—(CH₂)₄— H NCH₃ Ia1.49 CH₂ H CH₃ NC₂H₅ Ia1.50 CH₂ H H NC₂H₅ Ia1.51 C(CH₃)₂ H H NC₂H₅ Ia1.52 CH₂ H C₂H₅ NC₂H₅ Ia1.53 CH₂ CH₃ CH₃ NC₂H₅ Ia1.54 CH(CH₃) H CH₃ NC₂H₅ Ia1.55 CH(C₂H₅) H CH₃ NC₂H₅ Ia1.56 CH[CH(CH₃)₂] H H NC₂H₅ Ia1.57 CH₂ H CH(CH₃)₂ NC₂H₅ Ia1.58 CH(C₂H₅) H C₂H₅ NC₂H₅ Ia1.59 —CH—(CH₂)₄— H NC₂H₅ Ia1.60 CH₂ ═O S Ia1.61 CH(CH₃) ═O S Ia1.62 CH(C₂H₅) ═O S Ia1.63 CH[CH(CH₃)₂] ═O S Ia1.64 C(CH₃)₂ ═O S Ia1.65 CCH₃(C₂H₅) ═O S Ia1.66 CCH₃[CH(CH₃)₂] ═O S Ia1.67 CH₂ ═O NH Ia1.68 CH(CH₃) ═O NH Ia1.69 CH(C₂H₅) ═O NH Ia1.70 CH[CH(CH₃)₂] ═O NH Ia1.71 C(CH₃)₂ ═O NH Ia1.72 CCH₃(C₂H₅) ═O NH Ia1.73 CCH₃[CH(CH₃)₂] ═O NH Ia1.74 CH₂ ═O NCH₃ Ia1.75 CH(CH₃) ═O NCH₃ Ia1.76 CH(C₂H₅) ═O NCH₃ Ia1.77 CH[CH(CH₃)₂] ═O NCH₃ Ia1.78 C(CH₃)₂ ═O NCH₃ Ia1.79 CCH₃(C₂H₅) ═O NCH₃ Ia1.80 CCH₃[CH(CH₃)₂] ═O NCH₃ Ia1.81 O COOCH₃ H CH₂ Ia1.82 O COOC₂H₅ H CH₂ Ia1.83 O CONHCH₃ H CH₂ Ia1.84 O CON(CH₃)₂ H CH₂ Ia1.85 O CONHC₂H₅ H CH₂ Ia1.86 O CON(C₂H₅)₂ H CH₂ Ia1.87 O CH₃ H CH₂ Ia1.88 O C₂H₅ H CH₂ Ia1.89 O CH(CH₃)₂ H CH₂ Ia1.90 O COC₂H₅ H CH₂ Ia1.91 O CH₂CN H CH₂ Ia1.92 O CH₂N(CH₃)₂ H CH₂ Ia1.93 O CH₂ON═C(CH₃)₂ H CH₂ Ia1.94 O CH(OC₂H₅)₂ H CH₂ Ia1.95 O CH(OCH₃)₂ H CH₂ Ia1.96 O CH₃ CH₃ CH₂ Ia1.97 O CH₃ C₂H₅ CH₂ Ia1.98 O C₂H₅ C₂H₅ CH₂ Ia1.99 O —(CH₂)₄— CH₂ Ia1.100 O —(CH₂)₂—O—(CH₂)₂— CH₂ Ia1.101 O H —(CH₂)₃—CH— Ia1.102 O H —(CH₂)₄—CH— Ia1.103 O CH₃ H CHCH₃ Ia1.104 S ═O O Ia1.105 CH₂ ═S S Ia1.106 CH(CH₃) ═S S Ia1.107 CH(C₂H₅) ═S S Ia1.108 C(CH₃)₂ ═S S Ia1.109 O ═O NH Ia1.110 O ═O NCH₃ Ia1.111 O CH₃ H NH Ia1.112 O C₂H₅ H NH Ia1.113 O CH₃ CH₃ NH Ia1.114 O C₂H₅ C₂H₅ NH Ia1.115 O CH₃ H NCH₃ Ia1.116 O C₂H₅ H NCH₃ Ia1.117 O CH₃ CH₃ NCH₃ Ia1.118 O C₂H₅ C₂H₅ NCH₃ Ia1.119 NH ═O NH Ia1.120 NH ═O NCH₃ Ia1.121 NCH₃ ═O NH Ia1.122 NCH₃ ═O NCH₃ Ia1.123 NC₂H₅ ═O NH Ia1.124 NC₂H₅ ═O NC₂H₅

In addition, the following benzoyl derivatives of the formula I are particularly extraordinarily preferred:

-   -   The compounds Ia2.1-Ia2.124, which differ from the corresponding         compounds Ia1.1-Ia1.124 by the fact that R¹⁶ is ethyl and R¹⁸ is         hydrogen.

Also particularly extraordinarily preferred are the compounds Ib1 ({circumflex over (=)} I where R¹, R²=Cl, R³=H, R¹⁶, R¹⁸CH₃, Z=H) in particular the compounds of Table 2

TABLE 2 Ib1

No. X R⁴ R⁵ Y Ib1.1 CH₂ H CH₃ O Ib1.2 CH₂ H H O Ib1.3 C(CH₃)₂ H H O Ib1.4 CH₂ H C₂H₅ O Ib1.5 CH₂ CH₃ CH₃ O Ib1.6 CH(CH₃) H CH₃ O Ib1.7 CH(C₂H₅) H CH₃ O Ib1.8 CH[CH(CH₃)₂] H H O Ib1.9 CH₂ H CH(CH₃)₂ O Ib1.10 CH(C₂H₅) H C₂H₅ O Ib1.11 —CH—(CH₂)₄— H O Ib1.12 C═O CH₃ CH₃ O Ib1.13 C═O H C₂H₅ O Ib1.14 C═O C₂H₅ C₂H₅ O Ib1.15 C═O H H O Ib1.16 C═O H CH₃ O Ib1.17 CH₂ H CH₃ S Ib1.18 CH₂ H H S Ib1.19 C(CH₃)₂ H H S Ib1.20 CH₂ H C₂H₅ S Ib1.21 CH₂ CH₃ CH₃ S Ib1.22 CH(CH₃) H CH₃ S Ib1.23 CH(C₂H₅) H CH₃ S Ib1.24 CH(C₂H₅) H C₂H₅ S Ib1.25 —CH—(CH₂)₄— H S Ib1.26 CH[CH(CH₃)₂] H H S Ib1.27 CH₂ H CH(CH₃)₂ S Ib1.28 CH₂ H CH₃ NH Ib1.29 CH₂ H H NH Ib1.30 C(CH₃)₂ H H NH Ib1.31 CH₂ H C₂H₅ NH Ib1.32 CH₂ CH₃ CH₃ NH Ib1.33 CH(CH₃) H CH₃ NH Ib1.34 CH(C₂H₅) H CH₃ NH Ib1.35 CH(C₂H₅) H C₂H₅ NH Ib1.36 —CH—(CH₂)₄— H NH Ib1.37 CH[CH(CH₃)₂] H H NH Ib1.38 CH₂ H CH(CH₃)₂ NH Ib1.39 CH₂ H CH₃ NCH₃ Ib1.40 CH₂ H H NCH₃ Ib1.41 C(CH₃)₂ H H NCH₃ Ib1.42 CH₂ H C₂H₅ NCH₃ Ib1.43 CH₂ CH₃ CH₃ NCH₃ Ib1.44 CH(CH₃) H CH₃ NCH₃ Ib1.45 CH(C₂H₅) H CH₃ NCH₃ Ib1.46 CH[CH(CH₃)₂] H H NCH₃ Ib1.47 CH₂ H CH(CH₃)₂ NCH₃ Ib1.48 CH(C₂H₅) H C₂H₅ NCH₃ Ib1.49 —CH—(CH₂)₄— H NCH₃ Ib1.50 CH₂ H CH₃ NC₂H₅ Ib1.51 CH₂ H H NC₂H₅ Ib1.52 C(CH₃)₂ H H NC₂H₅ Ib1.53 CH₂ H C₂H₅ NC₂H₅ Ib1.54 CH₂ CH₃ CH₃ NC₂H₅ Ib1.55 CH(CH₃) H CH₃ NC₂H₅ Ib1.56 CH(C₂H₅) H CH₃ NC₂H₅ Ib1.57 CH[CH(CH₃ ₂] H H NC₂H₅ Ib1.58 CH₂ H CH(CH₃)₂ NC₂H₅ Ib1.59 CH(C₂H₅) H C₂H₅ NC₂H₅ Ib1.60 —CH—(CH₂)₄— H NC₂H₅ Ib1.61 CH₂ ═O S Ib1.62 CH(CH₃) ═O S Ib1.63 CH(C₂H₅) ═O S Ib1.64 CH[CH(CH₃ ₂] ═O S Ib1.65 C(CH₃)₂ ═O S Ib1.66 CCH₃(C₂H₅) ═O S Ib1.67 CCH₃[CH(CH₃)₂] ═O S Ib1.68 CH₂ ═O NH Ib1.69 CH(CH₃) ═O NH Ib1.70 CH(C₂H₅) ═O NH Ib1.71 CH[CH(CH₃ ₂] ═O NH Ib1.72 C(CH₃)₂ ═O NH Ib1.73 CCH₃(C₂H₅) ═O NH Ib1.74 CCH₃[CH(CH₃)₂] ═O NH Ib1.75 CH₂ ═O NCH₃ Ib1.76 CH(CH₃) ═O NCH₃ Ib1.77 CH(C₂H₅) ═O NCH₃ Ib1.78 CH[CH(CH₃ ₂] ═O NCH₃ Ib1.79 C(CH₃)₂ ═O NCH₃ Ib1.80 CCH₃(C₂H₅) ═O NCH₃ Ib1.81 CCH₃[CH(CH₃)₂] ═O NCH₃ Ib1.82 O COOCH₃ H CH₂ Ib1.83 O COOC₂H₅ H CH₂ Ib1.84 O CONHCH₃ H CH₂ Ib1.85 O CON(CH₃)₂ H CH₂ Ib1.86 O CONHC₂H₅ H CH₂ Ib1.87 O CON(C₂H₅)₂ H CH₂ Ib1.88 O CH₃ H CH₂ Ib1.89 O C₂H₅ H CH₂ Ib1.90 O CH(CH₃)₂ H CH₂ Ib1.91 O COC₂H₅ H CH₂ Ib1.92 O CH₂CN H CH₂ Ib1.93 O CH₂N(CH₃)₂ H CH₂ Ib1.94 O CH₂ON═C(CH₃)₂ H CH₂ Ib1.95 O CH(OC₂H₅)₂ H CH₂ Ib1.96 O CH(OCH₃)₂ H CH₂ Ib1.97 O CH₃ CH₃ CH₂ Ib1.98 O CH₃ C₂H₅ CH₂ Ib1.99 O C₂H₅ C₂H₅ CH₂ Ib1.100 O —(CH₂)₄— CH₂ Ib1.101 O —(CH₂)₂—O—(CH₂)₂— CH₂ Ib1.102 O H —(CH₂)₃—CH— Ib1.103 O H —(CH₂)₄—CH— Ib1.104 O CH₃ H CHCH₃ Ib1.105 O H H CH₂ Ib1.106 S ═O O Ib1.107 CH₂ ═S S Ib1.108 CH(CH₃) ═S S Ib1.109 CH(C₂H₅) ═S S Ib1.110 C(CH₃)₂ ═S S Ib1.111 O ═O NH Ib1.112 O ═O NCH₃ Ib1.113 O CH₃ H NH Ib1.114 O C₂H₅ H NH Ib1.115 O CH₃ CH₃ NH Ib1.116 O C₂H₅ C₂H₅ NH Ib1.117 O CH₃ H NCH₃ Ib1.118 O C₂H₅ H NCH₃ Ib1.119 O CH₃ CH₃ NCH₃ Ib1.120 O C₂H₅ C₂H₅ NCH₃ Ib1.121 NH ═O NH Ib1.122 NH ═O NCH₃ Ib1.123 NCH₃ ═O NH Ib1.124 NCH₃ ═O NCH₃ Ib1.125 NC₂H₅ ═O NH Ib1.126 NC₂H₅ ═O NC₂H₅

In addition, the following 3-heterocyclyl-substituted benzoyl derivatives of the formula I are particularly extraordinarily preferred:

-   -   The compounds Ib2.1-Ib2.126, which differ from the corresponding         compounds Ib1.1-Ib1.126 by the fact that R² is nitro.

-   -   The compounds Ib3.1-Ib3.126, which differ from the corresponding         compounds Ib1.1-Ib1.126 by the fact that R¹ is methyl and R² is         methylsulfonyl.

-   -   The compounds Ib4.1-Ib4.126, which differ from the corresponding         compounds Ib1.1-Ib1.126 by the fact R¹ is hydrogen and R² is         methylsulfonyl.

-   -   The compounds Ib5.1-Ib5.126, which differ from the corresponding         compounds Ib1.1-Ib1.126 by the fact that R¹ is trifluoromethyl         and R² is methylsulfonyl.

-   -   The compounds Ib6.1-Ib6.126, which differ from the corresponding         compounds Ib1.1-Ib1.126 by the fact that R¹ is methylsulfonyl.

-   -   The compounds Ib7.1-Ib7.126, which differ from the corresponding         compounds Ib1.1-Ib1.126 by the fact that R¹ is nitro.

-   -   The compounds Ib8.1-Ib8.126, which differ from the corresponding         compounds Ib1.1-Ib1.126 by the fact that R² is trifluoromethyl.

-   -   The compounds Ib9.1-Ib9.126, which differ from the corresponding         compounds Ib1.1-Ib1.126 by the fact that R² is methylthio.

-   -   The compounds Ib10.1-Ib10.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfinyl.

-   -   The compounds Ib11.1-Ib11.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         trifluoromethylsulfonyl.

-   -   The compounds Ib12.1-Ib12.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy and R² is methylsulfonyl.

-   -   The compounds Ib13.1-Ib13.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl.

-   -   The compounds Ib14.1-Ib14.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact R² is         methylsulfonyl and R³ is methyl.

-   -   The compounds Ib15.1-Ib15.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl and R³ is chlorine.

-   -   The compounds Ib16.1-Ib16.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl and R³ is chlorine.

-   -   The compounds Ib17.1-Ib17.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl and R³ is methyl.

-   -   The compounds Ib18.1-Ib18.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl.

-   -   The compounds Ib19.1-Ib19.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl and R² is hydrogen.

-   -   The compounds Ib20.1-Ib20.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact R¹ is methyl         and R² is nitro.

-   -   The compounds Ib21.1-Ib21.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib22.1-Ib22.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro and R¹⁸ is hydrogen.

-   -   The compounds Ib23.1-Ib23.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib24.1-Ib24.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         hydrogen, R² is methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib25.1-Ib25.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         trifluoromethyl, R² is methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib26.1-Ib26.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib27.1-Ib27.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact R¹ is nitro         and R¹⁸ is hydrogen.

-   -   The compounds Ib28.1-Ib28.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         trifluoromethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib29.1-Ib29.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylthio and R¹⁸ is hydrogen.

-   -   The compounds Ib30.1-Ib30.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfinyl and R¹⁸ is hydrogen.

-   -   The compounds Ib31.1-Ib31.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         trifluoromethylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib32.1-Ib32.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib33.1-Ib33.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib34.1-Ib34.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R³ is methyl and R¹⁸ is hydrogen.

-   -   The compounds Ib35.1-Ib35.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R³ is chlorine and R¹⁸ is hydrogen.

-   -   The compounds Ib36.1-Ib36.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R³ is chlorine and R¹⁸ is         hydrogen.

-   -   The compounds Ib37.1-Ib37.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R³ is methyl and R¹⁸ is hydrogen.

-   -   The compounds Ib38.1-Ib38.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl and R¹⁸ is hydrogen.

-   -   The compounds Ib39.1-Ib39.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is hydrogen and R¹⁸ is hydrogen.

-   -   The compounds Ib40.1-Ib40.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is nitro and R¹⁸ is hydrogen.

-   -   The compounds Ib41.1-Ib41.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib42.1-Ib42.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib43.1-Ib43.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         hydrogen, R² is methylsulfonyl, R¹⁶ is ethyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib44.1-Ib44.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         trifluoromethyl, R² is methylsulfonyl, R¹⁶ is ethyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib45.1-Ib45.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib46.1-Ib46.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib47.1-Ib47.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         trifluoromethyl, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib48.1-Ib48.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylthio, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib49.1-Ib49.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfinyl, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib50.1-Ib50.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         trifluoromethylsulfonyl, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib51.1-Ib51.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib52.1-Ib52.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib53.1-Ib53.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R³ is methyl, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib54.1-Ib54.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R³ is chlorine, R¹⁶ is ethyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib55.1-Ib55.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R³ is chlorine, R¹⁶ is ethyl and         R¹⁸ is hydrogen.

-   -   The compounds Ib56.1-Ib56.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R³ is methyl, R¹⁶ is ethyl and R¹⁸         is hydrogen.

-   -   The compounds Ib57.1-Ib57.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib58.1-Ib58.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is hydrogen, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib59.1-Ib59.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is nitro, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib60.1-Ib60.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R¹⁶ is n-propyl and R¹⁸ is hydrogen.

-   -   The compounds Ib61.1-Ib61.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, R¹⁶ is n-propyl and R¹⁸ is hydrogen.

-   -   The compounds Ib62.1-Ib62.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R¹⁶ is n-propyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib63.1-Ib63.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         hydrogen, R² is methylsulfonyl, R¹⁶ is n-propyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib64.1-Ib64.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         trifluoromethyl, R² is methylsulfonyl, R¹6 is n-propyl and R¹⁸         is hydrogen.

-   -   The compounds Ib65.1-Ib65.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R¹⁶ is n-propyl and R¹⁸ is hydrogen.

-   -   The compounds Ib66.1-Ib66.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R¹⁶ is n-propyl and R¹⁸ is hydrogen.

-   -   The compounds Ib67.1-Ib67.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         trifluoromethyl, R¹⁶ is n-propyl and R¹⁸ is hydrogen.

-   -   The compounds Ib68.1-Ib68.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylthio, R¹⁶ is n-propyl and R¹⁸ is hydrogen.

-   -   The compounds Ib69.1-Ib69.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfinyl, R¹⁶ is n-propyl and R¹⁸ is hydrogen.

-   -   The compounds Ib70.1-Ib70.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         trifluoromethylsulfonyl, R¹⁶ is n-propyl and R¹⁸ is hydrogen.

-   -   The compounds Ib71.1-Ib71.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, R¹6 is n-propyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib72.1-Ib72.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, R¹⁶ is n-propyl and R¹⁸ is hydrogen.

-   -   The compounds Ib73.1-Ib73.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R³ is methyl, R¹⁶ is n-propyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib74.1-Ib74.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R³ is chlorine, R¹⁶ is n-propyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib75.1-Ib75.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R³ is chlorine, R¹⁶ is n-propyl         and R¹⁸ is hydrogen.

-   -   The compounds Ib76.1-Ib76.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R³ is methyl, R¹⁶ is n-prcpyl and         R¹⁸ is hydrogen.

-   -   The compounds Ib77.1-Ib77.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R¹⁶ is n-propyl and R¹⁸ is hydrogen.

-   -   The compounds Ib78.1-Ib78.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is hydrogen, R¹⁶ is n-propyl and R¹⁸ is hydrogen.

-   -   The compounds Ib79.1-Ib79.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is nitro, R¹⁶ is n-propyl and R¹⁸ is hydrogen.

-   -   The compounds Ib80.1-Ib80.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹⁶ is         n-propyl and R¹⁸ is hydrogen.

-   -   The compounds Ib81.1-Ib81.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R¹⁶ is n-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib82.1-Ib82.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, R¹⁶ is n-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib83.1-Ib83.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R¹⁶ is n-butyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib84.1-Ib84.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         hydrogen, R² is methylsulfonyl, R¹⁶ is n-butyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib85.1-Ib85.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         trifluoromethyl, R² is methylsulfonyl, R¹⁶ is n-butyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib86.1-Ib86.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R¹⁶ is n-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib87.1-Ib87.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R¹⁶ is n-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib88.1-Ib88.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         trifluoromethyl, R¹⁶ is n-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib89.1-Ib89.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylthio, R¹⁶ is n-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib90.1-Ib90.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfinyl, R¹⁶ is n-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib91.1-Ib91.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         trifluoromethylsulfonyl, R¹⁶ is n-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib92.1-Ib92.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, R¹⁶ is n-butyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib93.1-Ib93.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, R¹⁶ is n-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib94.1-Ib94.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R³ is methyl, R¹⁶ is n-butyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib95.1-Ib95.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R³ is chlorine, R¹⁶ is n-butyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib96.1-Ib96.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R³ is chlorine, R¹⁶ is n-butyl and         R¹⁸ is hydrogen.

-   -   The compounds Ib97.1-Ib97.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R³ is methyl, R¹⁶ is n-butyl and         R¹⁸ is hydrogen.

-   -   The compounds Ib98.1-Ib98.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R¹⁶ is n-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib99.1-Ib99.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is hydrogen, R¹⁶ is n-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib100.1-Ib100.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is nitro, R¹⁶ is n-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib101.1-Ib101.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹⁶ is         n-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib102.1-Ib102.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R¹⁶ is iso-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib103.1-Ib10 3.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, R¹⁶ is iso-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib104.1-Ib104.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R¹⁶ is iso-butyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib105.1-Ib105.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         hydrogen, R² is methylsulfonyl, R¹⁶ is iso-butyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib106.1-Ib106.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         trifluoromethyl, R² is methylsulfonyl, R¹⁶ is iso-butyl and R¹⁸         is hydrogen.

-   -   The compounds Ib107.1-Ib107.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R¹⁶ is iso-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib108.1-Ib108.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R¹⁶ is iso-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib109.1-Ib109.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         trifluoromethyl, R¹⁶ is iso-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib110.1-Ib110.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylthio, R¹⁶ is iso-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib111.1-Ib111.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfinyl, R¹⁶ is iso-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib112.1-Ib112.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         trifluoromethylsulfonyl, R¹⁶ is iso-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib113.1-Ib113.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, R¹⁶ is iso-butyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib114.1-Ib114.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, R¹⁶ is iso-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib115.1-Ib115.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R³ is methyl, R¹⁶ is iso-butyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib116.1-Ib116.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R³ is chlorine, R¹⁶ is iso-butyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib117.1-Ib117.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R³ is chlorine, R¹⁶ is iso-butyl         and R¹⁸ is hydrogen.

-   -   The compounds Ib118.1-Ib118.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R³ is methyl, R¹⁶ is iso-butyl and         R¹⁸ is hydrogen.

-   -   The compounds Ib119.1-Ib119.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R¹⁶ is iso-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib120.1-Ib120.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is hydrogen, R¹⁶ is iso-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib121.1-Ib121.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is nitro, R¹⁶ is iso-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib122.1-Ib122.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹⁶ is         iso-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib123.1-Ib123.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact R¹ is         methylsulfonyl and R² is trifluoromethyl.

-   -   The compounds Ib124.1-Ib124.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R² is trifluoromethyl, and R¹⁸ is hydrogen.

-   -   The compounds Ib125.1-Ib125.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R² is trifluoromethyl, R¹⁶ is n-propyl and R¹⁸         is hydrogen.

-   -   The compounds Ib126.1-Ib126.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R² is trifluoromethyl, R¹⁶ is n-butyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib127.1-lbl27.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R² is trifluoromethyl, R¹⁶ is iso-butyl and R¹⁸         is hydrogen.

-   -   The compounds Ib128.1-Ib128.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R² is trifluoromethyl, R¹⁶ is ethyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib129.1-Ib129.126, which differ from the         corresponding compounds Ib1.29.1-Ib129.126 by the fact that R¹         is nitro and R² is methylsulfonyl.

-   -   The compounds Ib130.1-Ib130.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R² is methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib131.1-Ib131.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R² is methylsulfonyl, R¹⁶ is n-propyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib132.1-Ib132.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R² is methylsulfonyl, R¹⁶ is n-butyl and R¹⁸ is hydrogen.

-   -   The compounds Ib133.1-Ib133.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R² is methylsulfonyl, R¹⁶ is iso-butyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib134.1-Ib134.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R² is methylsulfonyl, R¹⁶ is ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib135.1-Ib135.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹⁸ is         hydrogen.

-   -   The compounds Ib136.1-Ib136.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹⁶ is         ethyl and R¹⁸ is hydrogen.

-   -   The compounds Ib137.1-Ib137.126 which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that Z is         methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib138.1-Ib138.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, Z is methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib139.1-Ib139.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, Z is methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib140.1-Ib140.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl , Z is methylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib141.1-Ib141.126 which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, Z is methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib142.1-Ib142.126 which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, Z is methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib143.1-Ib143.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact R¹ is methoxy,         R² and Z are methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib144.1-Ib144.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, Z is methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib145.1-Ib145.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹⁶ is         ethyl, Z is methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib146.1-Ib146.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R¹⁶ is ethyl, Z is methylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib147.1-Ib147.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, R¹⁶ is ethyl, Z is methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib148.1-Ib148.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R¹⁶ is ethyl, Z is methylsulfonyl         and R¹⁸ is hydrogen.

-   -   The compounds Ib149.1-Ib149.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R¹⁶ is ethyl, Z is methylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib150.1-Ib150.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R¹⁶ is ethyl, Z is methylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib151.1-Ib151.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, R¹⁶ is ethyl, Z is methylsulfonyl         and R¹⁸ is hydrogen.

-   -   The compounds Ib152.1-Ib152.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, R¹⁶ is ethyl, Z is methylsulfonyl and R¹⁸ is         hydrogen.

The compounds lb153.1-Ib153.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that Z is methylsulfonyl.

-   -   The compounds Ib154.1-Ib154.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² and Z         are methylsulfonyl.

-   -   The compounds Ib155.1-Ib155.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro and Z is methylsulfonyl.

-   -   The compounds Ib156.1-Ib156.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² and Z are methylsulfonyl.

-   -   The compounds Ib157.1-Ib157.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ and Z         are methylsulfonyl.

-   -   The compounds Ib158.1-Ib158.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro and Z is methylsulfonyl.

-   -   The compounds Ib159.1-Ib159.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² and Z are methylsulfonyl.

-   -   The compounds Ib160.1-Ib160.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl and Z is methylsulfonyl.

-   -   The compounds Ib162.1-Ib162.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that Z is         ethylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib162.1-Ib162.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, Z is ethylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib163.1-Ib163.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, Z is ethylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib164.1-Ib164.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, Z is ethylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib165.1-Ib165.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, Z is ethylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib166.1-Ib166.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, Z is ethylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib167.1-Ib167.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, Z is ethylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib168.1-Ib168.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² and Z         are ethylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib169.1-Ib169.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹⁶ is         ethyl, Z is ethylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib170.1-Ib170.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R¹⁶ is ethyl, Z is ethylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib171.1-Ib171.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, R¹⁶ is ethyl, Z is ethylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib172.1-Ib172.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R¹⁶ is ethyl, Z is ethylsulfonyl         and R¹⁸ is hydrogen.

-   -   The compounds Ib173.1-Ib173.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R¹⁶ is ethyl, Z is ethylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib174.1-Ib174.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R¹⁶ is ethyl, Z is ethylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib175.1-Ib175.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, R¹⁶ is ethyl, Z is ethylsulfonyl         and R¹⁸ is hydrogen.

-   -   The compounds Ib176.1-Ib176.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, R¹⁶ is ethyl, Z is ethylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib177.1-Ib177.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that Z is         ethylsulfonyl.

-   -   The compounds Ib178.1-Ib178.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl and Z is ethylsulfonyl.

-   -   The compounds Ib179.1-Ib179.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro and Z is ethylsulfonyl.

-   -   The compounds Ib180.1-Ib180.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl and Z is ethylsulfonyl.

-   -   The compounds Ib181.1-Ib181.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl and Z is ethylsulfonyl.

-   -   The compounds Ib182.1-Ib182.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro and Z is ethylsulfonyl.

-   -   The compounds Ib183.1-Ib183.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl and Z is ethylsulfonyl.

-   -   The compounds Ib184.1-lbl84.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² and Z         are ethylsulfonyl.

-   -   The compounds Ib185.1-Ib185.126 which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that Z is         iso-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib186.1-Ib186.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, Z is iso-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib187.1-Ib187.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, Z is iso-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib188.1-Ib188.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, Z is iso-propylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib189.1-Ib189.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, Z is iso-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib190.1-Ib190.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, Z is iso-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib191.1-Ib191.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, Z is iso-propylsulfonyl and R¹⁸         is hydrogen.

-   -   The compounds Ib192.1-Ib192.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, Z is iso-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib193.1-Ib193.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹⁶ is         ethyl, Z is iso-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib194.1-Ib194.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R¹⁶ is ethyl, Z is iso-propylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib195.1-Ib195.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, R¹⁶ is ethyl, Z is iso-propylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib196.1-Ib196.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R¹⁶ is ethyl, Z is         iso-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib197.1-Ib197.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R¹⁶ is ethyl, Z is iso-propylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib198.1-Ib198.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R¹⁶ is ethyl, Z is iso-propylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib199.1-Ib199.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, R¹⁶ is ethyl, Z is         iso-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib200.1-Ib200.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, R¹⁶ is ethyl, Z is iso-propylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib201.1-Ib201.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that Z is         n-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib202.1-Ib202.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, Z is n-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib203.1-Ib203.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, Z is n-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib204.1-Ib204.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, Z is n-propylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib205.1-Ib205.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, Z is n-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib206.1-Ib206.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, Z is n-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib207.1-Ib207.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, Z is n-propylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib.208.1-Ib208.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, Z is n-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib209.1-Ib209.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹⁶ is         ethyl, Z is n-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib210.1-Ib210.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R¹⁶ is ethyl, Z is n-propylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib211.1-Ib211.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, R¹⁶ is ethyl, Z is n-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib212.1-Ib212.126, which differ from the         corresponding compounds Ib212.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R¹⁶ is ethyl, Z is         n-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib213.1-Ib213.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R¹⁶ is ethyl, Z is n-propylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib214.1-Ib214.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R¹⁶ is ethyl, Z is n-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib215.1-Ib215.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, R¹⁶ is ethyl, Z is         n-propylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib216.1-Ib216.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, R¹⁶ is ethyl, Z is n-propylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib217.1-Ib217.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that Z is         n-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib218.1-Ib218.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, Z is n-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib219.1-Ib219.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, Z is n-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib220.1-Ib220.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, Z is n-butylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib221.1-Ib221.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, Z is n-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib222.1-Ib222.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, Z is n-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib223.1-Ib223.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, Z is n-butylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib224.1-Ib224.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, Z is n-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib225.1-Ib225.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹⁶ is         ethyl, Z is n-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib226.1-Ib226.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R¹⁶ is ethyl, Z is n-butylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib227.1-Ib227.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, R¹⁶ is ethyl, Z is n-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib228.1-Ib228.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R¹⁶ is ethyl, Z is n-butylsulfonyl         and R¹⁸ is hydrogen.

-   -   The compounds Ib229.1-Ib229.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R¹⁶ is ethyl, Z is n-butylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib230.1-Ib230.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R¹⁶ is ethyl, Z is n-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib231.1-Ib231.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, R¹⁶ is ethyl, Z is         n-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib232.1-Ib232.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, R¹⁶ is ethyl, Z is n-butylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib233.1-Ib233.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that Z is         iso-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib234.1-Ib234.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, Z is iso-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib235.1-Ib235.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, Z is iso-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib236.1-Ib236.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, Z is iso-butylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib237.1-Ib237.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, Z is iso-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib238.1-Ib238.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, Z is iso-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib239.1-Ib239.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, Z is iso-butylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib240.1-Ib240.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, Z is iso-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib241.1-Ib241.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹⁶ is         ethyl, Z is iso-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib242.1-Ib242.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R¹⁶ is ethyl, Z is iso-butylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib243.1-Ib243.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         nitro, R¹⁶ is ethyl, Z is iso-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib244.1-Ib244.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R¹⁶ is ethyl, Z is         iso-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib245.1-Ib245.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methylsulfonyl, R¹⁶ is ethyl, Z is iso-butylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib246.1-Ib246.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         nitro, R¹⁶ is ethyl, Z is iso-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib247.1-Ib247.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methoxy, R² is methylsulfonyl, R¹⁶ is ethyl, Z is         iso-butylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib248.1-Ib248.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R¹⁶ is ethyl, Z is iso-butylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib249.1-Ib249.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that Z is         phenylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib250.1-Ib250.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, Z is phenylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib251.1-Ib251.126 which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, Z is phenylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib252.1-Ib252.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, Z is phenylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib253.1-Ib253.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹⁶ is         ethyl, Z is phenylsulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib254.1-Ib254.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R¹⁶ is ethyl, Z is phenylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib255.1-Ib255.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R¹⁶ is ethyl, Z is phenylsulfonyl         and R¹⁸ is hydrogen.

-   -   The compounds Ib256.1-Ib256.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, R¹⁶ is ethyl, Z is phenylsulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib257.1-Ib257.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that Z is         p-toluenesulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib258.1-Ib258.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, Z is p-toluenesulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib259.1-Ib259.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, Z is p-toluenesulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib260.1-Ib260.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, Z is p-toluenesulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib261.1-Ib261.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹⁶ is         ethyl, Z is p-toluenesulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib262.1-Ib262.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         methylsulfonyl, R¹⁶ is ethyl, Z is p-toluenesulfonyl and R¹⁸ is         hydrogen.

-   -   The compounds Ib263.1-Ib263.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R¹ is         methyl, R² is methylsulfonyl, R¹⁶ is ethyl, Z is         p-toluenesulfonyl and R¹⁸ is hydrogen.

-   -   The compounds Ib264-Ib264.126, which differ from the         corresponding compounds Ib1.1-Ib1.126 by the fact that R² is         ethylsulfonyl, R¹⁶ is ethyl, Z is p-toluenesulfonyl and R¹⁸ is         hydrogen.

Also particularly preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where:

-   R¹ is halogen, C₁–C₆-alkyl, C₁–C₆-alkylthio or C₁–C₆-alkylsulfonyl;     in particular chlorine, methyl, methylthio or methylsulfonyl; -   R² is hydrogen, nitro, halogen, C₁–C₆-alkylthio, C₁–C₆-alkylsulfinyl     or C₁–C₆-alkylsulfonyl; in particular hydrogen, nitro, chlorine,     methylthio, methylsulfinyl, methylsulfonyl, ethylsulfonyl or     propylsulfonyl; -   R³ is hydrogen; -   R⁴, R⁵ are hydrogen, halogen, C₁–C₄-alkyl, C₁–C₄-haloalkyl,     C₁–C₄-alkoxy, C₁–C₄-alkylthio or COR⁶; in particular hydrogen,     fluorine, methyl, ethyl, propyl, trifluoromethyl, chloromethyl,     1-chloroeth-1-yl, methoxy, ethoxy, ethylthio or ethoxycarbonyl; or -   R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono-     to polysubstituted by C₁–C₄-alkyl and/or which can be interrupted by     oxygen or by a nitrogen which is unsubstituted or substituted by     C₁–C₄-alkyl; -   R⁶ is C₁–C₄-alkoxy; in particular ethyl; -   X is O or CR¹⁰R¹¹; -   Y is O, S or CR¹³R¹⁴; -   R¹⁰, R¹¹, R¹³, R¹⁴ are hydrogen, C₁–C₄-alkyl or C₁–C₄-haloalkyl; in     particular hydrogen, methyl or chloromethyl; or -   R⁵ and R¹³ together form a C₂–C₆-alkanediyl chain which can be mono-     to polysubstituted by C₁–C₄-alkyl and/or which can be interrupted by     oxygen or by a nitrogen which is unsubstituted or substituted by     C₁–C₄-alkyl; in particular 1,3-propanediyl; -   R¹⁶ is C₁–C₆-alkyl; in particular methyl, ethyl, propyl,     2-methylpropyl or butyl; -   Z is H or SO₂R¹⁷; -   R¹⁷ is C₁–C₄-alkyl; in particular methyl, ethyl, propyl or     2-methylpropyl;     with the exception of     4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1-ethyl-5-hydroxy-1H-pyrazole,     4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole,     4-[2-chloro-3-(5-cyano-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole     and     4-[2-chloro-3-(4,5-dihydrothiazol-2-yl)-4-methylsulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole;     and the agriculturally useful salts thereof; in particular alkali     metal salts and ammonium salts.

The 3-heterocyclyl-substituted benzoyl derivatives of the formula I are obtainable by various routes, for example by the following process:

Process A:

Reaction of pyrazoles of the formula II (where Z=H) with an activated benzoic acid IIIα or a benxoic acid IIIβ, which is preferably activated in situ to give the acylating product and subsequently subjecting the latter to a rearrangement reaction.

L¹ is a nucleophilically displaceable leaving group such as halogen, eg. bromine, chlorine, hetaryl, eg. imidazolyl, pyridyl, carboxylate, eg. acetate, trifluoroacetate, and the like.

The activated benzoic acid can be employed directly, as in the case of the benzoyl halides, or it can be prepared in situ, for example with dicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylic ester, 2-pyridine disulfide/triphenylphosphine, carbonyldiimidazole and the like.

It may be advantageous to carry out the acylation reaction in the presence of a base. The reactants and the auxiliary base are expediently employed in equimolar amounts. A small excess of the auxiliary base, for example 1.2 to 1.5 mol equivalents based on II, may be advantageous under certain circumstances.

Suitable auxiliary bases are tertiary alkylamines, pyridine or alkali metal carbonates. Examples of solvents which can be used are chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane, aromatic hydrocarbons such as toluene, xylene, chlorobenzene, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, polar aprotic solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, or esters such as ethyl acetate, or mixtures of these.

If benzoyl halides are employed as activated carboxylic acid component, it may be expedient to cool the reaction mixture to 0–10° C. when adding this reactant. The mixture is subsequently stirred at 20–100° C., preferably at 25–50° C., until the reaction is complete. Work-up is carried out in the customary manner, for example the reaction mixture is poured into water and the product of value is extracted. Especially suitable solvents for this purpose are methylene chloride, diethyl ether and ethyl acetate. After the organic phase has been dried and the solvent removed, the crude ester can be employed without further purification for the rearrangement reaction.

Rearrangement of the esters to give the compounds of the formula I is expediently carried out at from 20 to 40° C. in a solvent and in the presence of a base and, if appropriate, with the aid of a cyano compound as catalyst.

Examples of solvents which can be used are acetonitrile, methylene chloride, 1,2-dichlorethane, dioxane, ethyl acetate, toluene or mixtures of these. Preferred solvents are acetonitrile and dioxane.

Suitable bases are tertiary amines such triethylamine, pyridine, or alkali metal carbonates such as sodium carbonate, potassium carbonate, all of which are preferably employed in equimolar amounts or up to a fourfold excess, based on the ester. Triethylamine or alkali metal carbonate are preferably used, but by preference in a ratio of twice the equimolar amount based on the ester.

Suitable cyano compounds are inorganic cyanides such as sodium cyanide, potassium cyanide, and organic cyano compounds such as acetone cyanohydrin, trimethylsilyl cyanide. They are employed in an amount of from 1 to 50 mol percent, based on the ester. Substances which are preferably employed are acetone cyanohydrin or trimethylsilyl cyanide, for example in an amount of from 5 to 15, preferably 10, mol percent, based on the ester.

Work-up can be effected in a manner known per se. For example, the reaction mixture is acidified with dilute mineral acid, such as 5% strength hydrochloric acid or sulfuric acid, and extracted with an organic solvent, eg. methylene chloride or ethyl acetate. The organic extract can be extracted with 5–10% strength alkali metal carbonate solution, eg. sodium carbonate or potassium carbonate solution. The aqueous phase is acidified, and the precipitate which forms is filtered off with suction and/or extracted with methylene chloride or ethyl acetate, dried and concentrated.

(Examples of the synthesis of esters from hydroxypyrazoles and of the rearrangement of the esters are mentioned, for example, in EP-A 282 944 and U.S. Pat. No. 4,643,757).

Process B:

Reaction of 3-heterocyclyl-substituted benzoyl derivatives of the formula I (where Z=H) with a compound of the formula V (where Z=SO₂R¹⁷):

L² is a nucleophilically displaceable leaving group, such as halogen, eg. bromine, chlorine, hetaryl, eg. imidazolyl, pyridyl, sulfonate, eg. OSO₂R¹⁷.

The compounds of the formula V can be employed directly such as, for example, in the case of the sulfonyl halides or sulfonic anhydrides, or they can be prepared in situ, for example activated sulfonic acids (by means of sulfonic acid and dicyclohexylcarbodiimide, carbonyldiimidazole and the like).

As a rule, the starting compounds are employed in an equimolar ratio. However, it may also be advantageous to employ an excess of one or the other component.

It may be advantageous to carry out the reaction in the presence of a base. The reactants and the auxiliary base are expediently employed in equimolar ratios. An excess of the auxiliary base, for example 1.5 to 3 mol equivalents, based on II, may be advantageous under certain circumstances.

Suitable auxiliary bases are tertiary alkylamines such as triethylamine or pyridine, alkali metal carbonates, eg. sodium carbonate or potassium carbonate, and alkali metal hydrides, eg. sodium hydride. Triethylamine and pyridine are preferably used.

Examples of suitable solvents are chlorinated hydrocarbons such as methylene chloride or 1,2-dichlorethane, aromatic hydrocarbons, eg. toluene, xylene or chlorobenzene, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, polar aprotic solvents such as acetonitrile, dimethylformamide or dimethyl sulfoxide, or esters such as ethyl acetate, or mixtures of these.

As a rule, the reaction temperature is in the range of from 0° C. to the boiling point of the reaction mixture.

Work-up can be effected in a manner known per se to give the product.

Those pyrazoles of the formula II (where Z=H) which are used as starting materials and which are not already known can be prepared by processes known per se (for example EP-A 240 001 and J. Prakt. Chem. 315, 383 (1973)).

Novel 3-heterocyclyl-substituted benzoic acid derivatives of the formula III

are those where the variables have the following meanings:

-   R¹, R² are hydrogen, nitro, halogen, cyano, C₁–C₆-alkyl,     C₁–C₆-haloalkyl, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy, C₁–C₆-alkylthio,     C₁–C₆-haloalkylthio, C₁–C₆-alkylsulfinyl, C₁–C₆-haloalkylsulfinyl,     C₁–C₆-alkylsulfonyl or C₁–C₆-haloalkylsulfonyl; -   R³ is hydrogen, halogen or C₁–C₆-alkyl; -   R⁴, R⁵ are hydrogen, halogen, cyano, nitro, C₁–C₄-alkyl,     C₁–C₄-alkoxy-C₁–C₄-alkyl, di(C₁–C₄-alkoxy)-C₁–C₄-alkyl,     di(C₁–C₄-alkyl)amino-C₁–C₄-alkyl,     [2,2-di(C₁–C₄-alkyl)hydrazino-1]-C₁–C₄-alkyl,     C₁–C₆-alkyliminooxy-C₁–C₄ -alkyl, C₁–C₄-alkoxycarbonyl-C₁–C₄-alkyl,     C₁–C₄-alkylthio-C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-cyanoalkyl,     C₃–C₈-cycloalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy,     C₁–C₄-haloalkoxy, hydroxyl, C₁–C₄-alkylcarbonyloxy, C₁–C₄-alkylthio,     C₁–C₄-haloalkylthio, di(C₁–C₄-alkyl)amino, COR⁶, phenyl or benzyl,     it being possible for the two last-mentioned substituents to be     partially or fully halogenated and/or to have attached to them one     to three of the following groups:     -   nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or         C₁–C₄-haloalkoxy; or -   R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono-     to tetrasubstituted by C₁–C₄-alkyl and/or which can be interrupted     by oxygen or by a nitrogen which is unsubstituted or substituted by     C₁–C₄-alkyl; or -   R⁴ and R⁵ together with the corresponding carbon form a carbonyl or     a thiocarbonyl group; -   R⁶ is hydrogen, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy,     C₁–C₄-alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy, C₃–C₆-alkenyloxy,     C₃–C₆-alkynyloxy or NR⁷R⁸; -   R⁷ is hydrogen or C₁–C₄-alkyl; -   R⁸ is C₁–C₄-alkyl; -   X is O, S, NR⁹, CO or CR¹⁰R¹¹; -   Y Y is O, S, NR¹², CO or CR¹³R¹⁴; -   R⁹, R¹² are hydrogen or C₁–C₄-alkyl; -   R¹⁰, R¹¹, R¹³, R¹⁴ are hydrogen, C₁–C₄-alkyl, C₁–C₄-haloalkyl,     C₁–C₄-alkoxycarbonyl, C₁–C₄-haloalkoxycarbonyl or CONR⁷R⁸; or -   R⁴ and R⁹ or R⁴ and R¹⁰ or R⁵ and R¹² or R⁵ and R¹³ together form a     C₂–C₆-alkanediyl chain which can be mono- to tetrasubstituted by     C₁–C₄-alkyl and/or which can be interrupted by oxygen or by a     nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl; -   R¹⁹ is hydroxyl or a radical which can be removed by hydrolysis;     with the exception of methyl     2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate,     methyl 2-chloro-3-(4,5-dihydrooxazol-2-yl)-4-methylsulfonylbenzoate     and methyl     2,4-dichloro-3-(5-methylcarbonyloxy-4,5-dihydroisoxazol-3-yl)benzoate.

Examples of radicals which can be removed by hydrolysis are alkoxy, phenoxy, alkylthio and phenylthio radicals which are unsubstituted or substituted, halides, hetaryl radicals which are bonded via nitrogen; amino, imino radicals which are unsubstituted or substituted, and the like.

Preferred are 3-heterocyclyl-substituted benzoic acid halides of the formula IIIα′, where L¹′=halogen ({circumflex over (=)}III where R¹⁹=halogen)

where the variables R¹ to R⁵, X and Y have the meanings given under the formula III and

-   L¹′ is halogen, in particular chlorine or bromine.

Equally preferred are 3-heterocyclyl-substituted benzoic acids of the formula IIIβ ({circumflex over (=)}III where R¹⁹=hydroxyl)

where the variables R¹ to R⁵, X and Y have the meanings given under formula III.

Equally preferred are 3-heterocyclyl-substituted benzoic esters of the formula IIIγ ({circumflex over (=)}III where R¹⁹=C₁–C₆-alkoxy)

where the variables R¹ to R⁵, X and Y have the meanings given under formula III and

-   L³ is C₁–C₆-alkoxy.

The specially preferred embodiments of the 3-heterocyclyl-substituted benzoic acid derivatives of the formula III with regard to the variables R¹ to R⁵, X and Y correspond to those of the 3-heterocyclyl-substituted benzoyl derivatives of the formula I.

Also preferred are 3-heterocyclyl-substituted benzoic acid derivatives of the formula III, where:

-   R¹ is halogen, C₁–C₆-alkyl, C₁–C₆-alkylthio or C₁–C₆₋alkylsulfonyl;     in particular chlorine, methyl, methylthio or methylsulfonyl;     extraordinarily preferably chlorine; -   R² is hydrogen, nitro, halogen, C₁–C₆-alkylthio, C₁–C₆-alkylsulfinyl     or C₁–C₆-alkylsulfonyl; in particular hydrogen, nitro, chlorine,     methylthio, methylsulfinyl, methylsulfonyl, ethylsulfonyl or     propylsulfonyl; extraordinarily preferably hydrogen, chlorine,     methylthio, methylsulfonyl, ethylsulfonyl or propylsulfonyl; -   R³ is hydrogen; -   R⁴, R⁵ are hydrogen, halogen, C₁–C₄-alkyl, C₁–C₄-haloalkyl,     C₁–C₄-alkoxy, hydroxyl, C₁–C₄-alkylcarbonyloxy, C₁–C₄-alkylthio or     COR⁶; in particular hydrogen, fluorine, methyl, ethyl, propyl,     trifluoromethyl, chloromethyl, 2-chloroeth-1-yl, methoxy, ethoxy,     2-methylprop-1-oxy, hydroxyl, methylcarbonyloxy, ethylthio, formyl,     methylcarbonyl, methoxycarbonyl or ethoxycarbonyl; extraordinarily     preferably hydrogen, fluorine, methyl, ethyl, trifluoromethyl,     chloromethyl, 2-chloroeth-1-yl, methoxy, ethoxy, 2-methylprop-1-oxy,     hydroxyl, methylcarbonyloxy, ethylthio, formyl, methylcarbonyl,     methoxycarbonyl or ethoxycarbonyl; or -   R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono-     to polysubstituted by C₁–C₄-alkyl and/or which can be interrupted by     oxygen or by a nitrogen which is unsubstituted or substituted by     C₁–C₄-alkyl; in particular 1,4-butanediyl, 2-oxo-1,5-pentanediyl; or -   R⁴ and R⁵ together with the corresponding carbon atoms form a     carbonyl group -   R⁶ is hydrogen, C₁–C₄-alkyl or C₁–C₄-alkoxy; in particular hydrogen,     methyl, methoxy or ethoxy; -   X is O, S, CO, CR¹⁰R¹¹; -   Y is O, S, CR¹³R¹⁴; -   R¹⁰, R¹¹, R¹³, R¹⁴ are hydrogen, C₁–C₄-alkyl, C₁–C₄-haloalkyl or     C₁–C₄-alkoxycarbonyl; in particular hydrogen, methyl, chloromethyl     or methoxycarbonyl; or -   R⁵ and R¹³ together form a C₂–C₆-alkanediyl chain which can be mono-     to polysubstituted by C₁–C₄-alkyl and/or which can be interrupted by     oxygen or by a nitrogen which is unsubstituted or substituted by     C₁–C₄-alkyl; in particular 1,3-propanediyl; -   R¹⁹ is hydroxyl, halogen or C₁–C₆-alkoxy; in particular hydroxyl,     chlorine, methoxy or ethoxy;     with the exception of methyl     2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate,     methyl 2-chloro-3-(4,5-dihydrooxazol-2-yl)-4-methylsulfonylbenzoate     and methyl     2,4-dichloro-3-(5-methylcarbonyloxy-4,5-dihydroisoxazol-3-yl)benzoate.

The benzoyl halides of the formula IIIα′(where L¹′=Cl, Br) can be prepared in a manner known per se by reacting the benzoic acids of the formula IIIβ with halogenating reagents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride or oxalyl bromide.

The benzoic acids of the formula IIIβ can be prepared in a known manner from the corresponding esters of the formula IIIγ (L³=C₁–C₆-alkoxy) by means of acid or basic hydrolysis.

Equally, the benzoic acids of the formula IIIβ can be obtained by reacting corresponding bromine- or iodine-substituted compounds of the formula V, with carbon monoxide and water under elevated pressure in the presence of a palladium, nickel, cobalt or rhodium transition metal catalyst and a base.

Furthermore, it is possible to convert compounds of the formula V into the corresponding nitriles of the formula VI by a Rosenmund-von Braun reaction (cf., for example, Org. Synth. Vol III (1955), 212) and to convert these nitriles into the compounds of the formula IIIβ by subsequent hydrolysis.

The esters of the formula IIIγ can be obtained by reacting arylhalogen compounds or arylsulfonates of the formula VII, where L⁴ is a leaving group such as bromine, iodine, triflate, fluorosulfonyloxy and the like with heterocyclyl stannates (Stille couplings), heterocyclyl-boron compounds (Suzuki couplings) or heterocyclyl-zinc compounds (Negishi reaction) VIII, where M is Sn(C₁–C₄-alkyl)₃, B(OH)₂, ZnHal (where Hal=chlorine, bromine) and the like, respectively, in a manner known per se (cf., for example, Tetrahedron Lett. 27 (1986), 5269) in the presence of a palladium or nickel transition metal catalyst and in the presence or absence of a base.

Equally, it is possible to obtain esters of the formula IIIγ by synthesizing the heterocycle which is bonded in the 3-position.

For example, 1,2,4-oxadiazolin-3-yl derivatives (IIIγ where X═O, Y═NH) can be prepared from amidoximes of the formula IX by condensation with aldehydes or ketones (cf., for example, Arch. Phar. 326 (1993), 383–389).

Thioamides of the formula X are suitable precursors for 2-thiazolinyl derivatives I (where X═CR¹⁰R¹¹, Y═S) (cf., for example, Tetrahedron 42 (1986), 1449–1460).

2-Oxazolinyl, 2-thiazolinyl and 2-imidazolinyl derivatives (IIIγ where X═CR¹⁰R¹¹, Y═O or Y═S or Y═NH) are accessible from the carboxylic acids of the formula XI (cf., for example, Tetrahedron Let. 22 (1981), 4471–4474).

1,3-Thiazol-5(4H)-thion-2-yl (cf., for example, Helv. Chim. Acta 69 (1986), 374–388) and 5-oxo-2-imidazolin-2-yl derivatives (cf., for example, Heterocycles 29 (1989), 1185–1189) (III where X═CR¹⁰R¹¹, Y═S or Y═NH) can be prepared by processes known from the literature from carboxylic acid halides of the formula XII where Hal is halogen, in particular from carboxylic acid chlorides.

The oximes of the formula XIII can be converted into 4,5-dihydroisoxazol-3-yl derivatives (IIIγ where X═O, Y═CR¹³R¹⁴) in a manner known per se via the hydroxamic acid chlorides XIV as intermediates. From the latter, nitrile oxides are prepared in situ, and these nitrile oxides react with alkenes to give the desired products (cf., for example, Chem. Ber. 106 (1973), 3258–3274). 1,3-Dipolar cycloaddition reactions of chlorosulfonyl isocyanate with nitrile oxides yield 1,2,4-oxadiazolin-5-on-3-yl derivatives (IIIγ where X═O, Y═NH) (cf., for example, Heterocycles 27 (1988), 683–685).

The aldehydes of the formula XIV can be converted into 2,4-dihydro-1,2,4-triazol-3-on-5-yl derivatives (IIIγ where X═NR⁹, X═NR¹²) via the semicarbazones as intermediates (cf., for example, J. Heterocyclic Chem. 23 (1986), 881–883).

2-Imidazolinyl derivatives (IIIγ where X═CR¹⁰R¹¹, Y═NH) can also be prepared from benzonitriles of the formula XV using known methods (cf., for example, J. Org. Chem. 52 (1987), 1017–1021).

1,3-Dipolar cycloaddition reactions of diazoalkanes or nitriloimines with arylalkenes of the formula XVI can be used for synthesizing 3-pyrazolinyl derivatives (IIIγ where X═NH, Y═CHR¹³).

The bromine- or iodine-substituted compounds of the formula V which are used as starting compounds can be obtained from corresponding anilines by methods similar to those known from the literature, for example by Sandmeyer reaction, and the anilines, in turn, are synthesized by reducing suitable nitro compounds. The bromine-substituted compounds of the formula V can additionally be obtained by direct bromination of suitable starting materials (cf. Monatsh. Chem. 99 (1968), 815–822).

The nitriles of the formula VI can be obtained as described above. Equally, it is possible to synthesize them from corresponding anilines by means of a Sandmeyer reaction.

The starting compounds of the formula VII are known (cf., for example, Coll. Czech. Chem. Commun. 40 (1975), 3009–3019) or can be prepared readily by a suitable combination of known syntheses.

For example, the sulfonates VII (L⁴=OSO₂CF₃, OSO₂F) can be obtained from the corresponding phenols, which, in turn, are known (cf., for example, EP-A 195 247) or can be prepared by known methods (cf., for example, Synthesis 1993, 735–762).

The halogen compounds VII (L⁴=Cl, Br or I) can be obtained, for example, from the corresponding anilines of the formula XIX by a Sandmeyer reaction.

The amidoximes of the formula IX, the thioamides of the formula X and the carboxylic acids of the formula XI can be synthesized from the nitriles of the formula XV in a manner known per se.

Furthermore, it is possible to prepare the carboxylic acids of the formula XI from the aldehydes of the formula XIV by known processes (cf., for example, J. March, Advanced Organic Chemistry, 3rd edition (1985), p. 629 et seq., Wiley-Interscience Publication).

The carboxylic acid halides of the formula XII can be obtained from the corresponding carboxylic acids of the formula XI by methods similar to standard processes.

The oximes of the formula XIII are advantageously obtained by reacting aldehydes of the formula XIV with hydroxylamine in a manner known per se (cf., for example, J. March, Advanced Organic Chemistry, 3rd ed. (1985), pp. 805–806, Wiley-Interscience Publication).

Those aldehydes of the formula XIV which are not already known can be prepared by methods similar to known processes. Thus, they can be synthesized from methyl compounds of the formula XVII by means of bromination, for example with N-bromosuccinimide or 1,3-dibromo-5,5-dimethylhydantoin, followed by oxidation (cf. Synth. Commun. 22 (1992), 1967–1971).

The oximes of the formula XIII can also be converted into nitrites of the formula XV by processes which are known per se (cf., for example, J. March, Advanced Organic Chemistry, 3rd ed. (1985), pp. 931–932, Wiley-Interscience Publication).

Arylalkenes of the formula XVI can be synthesized starting from the halogen compounds or sulfonates of the formula VII (L⁴=Br, Cl, OSO₂CF₃, OSO₂F) by, inter alia, Heck reaction with olefins in the presence of a palladium catalyst (cf., for example, Heck, Palladium Reagents in Organic Synthesis, Academic Press, London 1985; Synthesis 1993, 735–762).

PREPARATION EXAMPLES 4-[2-Chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-5-hydroxy-1-methyl-1H-pyrazole (compound 3.35)

43.60 g (0.13 mol) of 2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl chloride in 375 ml of anhydrous dioxane and 13.56 g (0.134 mol) of triethylamine in 375 ml of anhydrous dioxane are simultanouesly added dropwise at room temperature under a protective gas atmosphere to a solution 12.74 g (0.13 mol) of 5-hydroxy-1-methylpyrazole and 300 ml of anhydrous dioxane. After the reaction mixture had been stirred for 2 hours at room temperature, it was filtered through silica gel and the residue was washed with dioxane. The eluate was concentrated in vacuo to approxmately 500 ml, and 17.94 g (0.13 mol) of dried, finely powdered potassium carbonate were added. After the mixture had been refluxed for 6 hours, the solvent was distilled off in vacuo and the residue was taken up in approximately 700 ml of water. Insoluble constituents were filtered off, and the pH of the filtrate was brought to 2–3 by slow addition of 10% strength hydrochloric acid. The precipitate which formed was filtered off with suction. This gave 46.16 g (92% of theory) of 4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-5-hydroxy-1-methyl-1H-pyrazole.

-   -   (m.p.>250° C.).

Table 3 shows the above compound and, in addition, other 3-heterocyclyl-substituted benzoyl derivatives of the formula I which were prepared, or can be prepared, in a similar manner (if the end products had not precipitated upon acidification with 10% strength hydrochloric acid, they were extracted with ethyl acetate or dichloromethane; the organic phase was subsequently dried and concentrated in vacuo):

TABLE 3

Physical data m.p. [° C.]; No. R¹ R² R³ X R⁴ R⁵ Y R¹⁶ Z R¹⁸ ¹H NMR [δ in ppm] 3.1 Cl Cl H O H H CH₂ n-C₄H₉ H H 116–117 3.2 Cl Cl H O H H CH₂ i-C₄H₉ H H 148–151 3.3 Cl Cl H O H H CH₂ n-C₄H₉ C₂H₅SO₂ H 0.95(t); 1.32(m); 1.62(t); 1.92(quin); 3.30(t) 3.78(quar); 4.17(t); 4.61(t); 7.42(d); 7.48(m). 3.4 Cl Cl H O H H CH₂ i-C₄H₉ i-C₄H₉SO₂ H 0.96(d); 1.21(d); 2.33(m); 2.48(m); 3.30(t); 3.67(d); 3.97(d); 4.58(t); 7.42(d); 7.50(m). 3.5 Cl Cl H O H H CH₂ n-C₃H₇ i-C₄H₉SO₂ H 0.97(t); 1.20(d); 1.96(m); 2.49(m); 3.30(t); 3.68(d); 4.12(t); 4.59(t); 7.42(d); 7.49(d); 7.52(s). 3.6 Cl Cl H O H H CH₂ n-C₃H₇ C₂H₅SO₂ H 0.97(t), 1.12(d); 1.63(t); 1.94(m); 3.29(t); 3.76(q); 4.14(t); 4.60(t); 7.42(d), 7.48(d); 7.51(s). 3.7 Cl SO₂CH₃ H O COOC₂H₅ H CH₂ CH₃ H H 70–75 3.8 Cl SO₂CH₃ H O COOC₂H₅ H CH₂ C₂H₅ H H 65–70 3.9 Cl SO₂CH₃ H O CH₃ H CH₂ CH₃ H H 230–235 3.10 Cl SO₂CH₃ H O CH₃ H CH₂ C₂H₅ H H 210–215 3.11 Cl SO₂CH₃ H O CH₃ H CH₂ n-C₃H₇ H H  95–100 3.12 Cl SO₂CH₃ H O CH₃ H CH₂ CH₃ C₂H₅SO₂ H 70–75 3.13 Cl SO₂CH₃ H O CH₃ H CH₂ C₂H₅ C₂H₅SO₂ H 78–83 3.14 Cl SO₂CH₃ H O CH₃ H CH₂ C₂H₅ i-C₄H₉SO₂ H 1,24(2d); 1.53(t); 2.52(m); 3.05(dd); 3.29(s); 3.52(dd); 3.73(d); 4.24(q), 5.05(m); 7.49(s); 7.66(d); 8.18(d). 3.15 Cl SO₂CH₃ H O CH₃ H CH₂ n-C₃H₇ C₂H₅SO₂ H 0.96(t); 1.53(d); 1.68(t); 1.95(sext); 3.07(dd); 3.32(s); 3.58 (dd); 3.86 (quart); 4.15(t); 5.03(m); 7.46(d); 7.64(d); 8.18(d). 3.16 Cl SO₂CH₃ H O CH₃ CH₃ CH₂ CH₃ H H 220–225 3.17 Cl SO₂CH₃ H O CH₃ CH₃ CH₂ C₂H₅ H H 82–86 3.18 Cl SO₂CH₃ H O CH₃ CH₃ CH₂ n-C₃H₇ H H 70–75 3.19 Cl SO₂CH₃ H O CH₃ CH₃ CH₂ n-C₄H₉ H H 68–73 3.20 Cl SO₂CH₃ H O CH₃ CH₃ CH₂ i-C₄H₉ H H 45–50 3.21 Cl SO₂CH₃ H O C₂H₅ H CH₂ CH₃ H H 220–225 3.22 Cl SO₂CH₃ H O C₂H₅ H CH₂ C₂H₅ H H 170–175 3.23 Cl SO₂CH₃ H O H H CH₂ n-C₃H₇ H H 65–70 3.24 Cl SO₂CH₃ H O H H CH₂ n-C₄H₉ H H 55–60 3.25 Cl SO₂CH₃ H O H H CH₂ i-C₄H₉ H H 58–63 3.26 Cl SO₂CH₃ H O H H CH₂ n-C₄H₉ C₂H₅SO₂ H 78–83 3.27 Cl SO₂CH₃ H O H H CH₂ n-C₄H₉ i-C₄H₉SO₂ H 0.94(t); 1.19(d); 1.22(t); 1.38(m); 1.74(br); 1.91(m); 2.53(m); 3.26(s); 4.45(t); 3.76(d); 4.18(t); 4.62(t); 7.45(s); 7.64(d); 8.16(d). 3.28 Cl SO₂CH₃ H O H H CH₂ i-C₄H₉ i-C₄H₉SO₂ H 0.96(d); 1.21(d); 2.33(m); 2.51(m); 3.28(s); 3.44(t); 3.75(d); 3.99(d); 4.61(t); 7.45(s); 7.66(d); 8.17(d). 3.29 Cl SO₂CH₃ H O H H CH₂ i-C₄H₉ C₂H₅SO₂ H 0.97(d); 1.66(t); 2.36(m); 3.29(s); 3.43(t); 3.82(q); 3.99(d); 4.60(t); 7.47(s); 7.68(d); 8.18(d). 3.30 Cl SO₂CH₃ H O H H CH₂ CH₃ C₂H₅SO₂ H 1.68(t); 3.29(s); 3.43(t); 3.78(q); 3.92(s); 3.63(t); 7.46(s); 7.62(d); 8.17(d). 3.31 Cl SO₂CH₃ H O H H CH₂ CH₃ i-C₄H₉SO₂ H 1.23(d); 2.53(m), 3.28(s); 3.43(t); 3.70(d); 3.91(s); 4.61(t); 7.48(s); 7.66(d); 8.18(d). 3.32 Cl Cl H O H H CH₂ n-C₃H₇ H H 119–121 3.33 Cl Cl H O H H CH₂ CH₃ H CH₃ 115–117 3.34 Cl NO₂ H O H H CH₂ C₂H₅ H H 217–218 3.35 Cl SO₂CH₃ H O H H CH₂ CH₃ H H >250 3.36 Cl Cl H O H H CH₂ C₂H₅ H H 125–128 3.37 Cl SO₂CH₃ H O H H CH₂ C₂H₅ n-C₂H₇SO₂ H 78–83 3.38 Cl SO₂CH₃ H O H H CH₂ C₂H₅ C₂H₅SO₂ H 1.52(t); 1.68(t); 3.29(s); 3.43(t); 3.82(q); 4.24(q); 4.63(t); 7.48(s); 7.65(d); 8.07(d). 3.39 Cl SO₂C₂H₅ H O CH₃ CH₃ CH₂ CH₃ H H >200 3.40 Cl SO₂C₂H₅ H O CH₃ H CH₂ CH₃ H H 220–223 3.41 Cl SO₂C₂H₅ H O CH₃ H CH₂ C₂H₅ H H >230 3.42 Cl SO₂-n-C₃H₇ H O CH₃ H CH₂ CH₃ H H 1.12(t); 1.53(d); 1.76(quin); 3.18(dd); 3.38(t); 3.55(dd); 3.73(s); 5.04(m); 5.55 (s,br.); 7.37(s); 7.68(d); 8.13(d). 3.43 Cl SO₂-n-C₃H₇ H O CH₃ H CH₂ C₂H₅ H H 1.07(t); 1.50(m); 1.78(quin); 3.07(dd); 3.39(t); 3.55(dd); 4.12(t); 5.08(m); 7.38(s); 7.69(d); 8.11(d). 3.44 Cl SO₂CH₃ H CH₂ H H O CH₃ H H 3.45 Cl SO₂CH₃ H C(CH₃)₂ H H O CH₃ H H 1.33(s); 3.40(s); a) 4.17(s); 7.43(s); 7.79(d); 8.04(d). 3.46 Cl SO₂CH₃ H O H H CH₂ C₂H₅ Na⁺ H 218–220 3.47 Cl SO₂CH₃ H O H H CH₂ C₂H₅ K⁺ H 193 3.48 Cl SO₂CH₃ H O H H CH₂ C₂H₅ Li⁺ H >230 3.49 Cl SO₂CH₃ H O H H CH₂ C₂H₅ NH₄ ⁺ H 170–175 3.50 Cl SO₂CH₃ H O H H CH₂ CH₃ Na⁺ H >240 3.51 Cl SO₂CH₃ H O H H CH₂ CH₃ K⁺ H 206–214 3.52 Cl SO₂CH₃ H O H H CH₂ CH₃ Li⁺ H >240 3.53 Cl SO₂CH₃ H O H H CH₂ CH₃ NH₄ ⁺ H 3.54 Cl SO₂CH₃ H C(CH₃)₂ H H O C₂H₅ H H 1.27(t); 1.36(s); a) 3.41(q); 4.01(q); 4.18(s); 7.47(s); 7.83(d); 8.07(d). 3.55 Cl SO₂CH₃ H O H —(CH₂)₃CH— C₂H₅ H H  99–104 3.56 Cl SO₂CH₃ H O H —(CH₂)₃CH— CH₃ H H  95–100 3.57 Cl SO₂CH₃ H O —(CH₂)₄— CH₂ CH₃ H H 230–235 3.58 Cl SO₂CH₃ H O —(CH₂)₄— CH₂ C₂H₅ H H 190–195 3.59 Cl SO₂CH₃ H O —(CH₂)₂O(CH₂)₂ CH₂ C₂H₅ H H  95–100 3.60 Cl SO₂C₂H₅ H O CH₃ CH₃ CH₂ CH₃ H H <230 3.61 Cl SO₂C₂H₅ H O CH₃ CH₃ CH₂ C₂H₅ H H 198–200 3.62 Cl SO₂C₂H₅ H O H H CH₂ CH₃ H H 215–218 3.63 Cl SO₂C₂H₅ H O H H CH₂ C₂H₅ H H 213–215 3.64 Cl SO₂-n-C₃H₇ H O H H CH₂ CH₃ H H 186–190 3.65 Cl SO₂-n-C₃H₇ H O H H CH₂ C₂H₅ H H 84–86 3.66 Cl SO₂CH₃ H O —(CH₂)₂O(CH₂)₂— CH₂ CH₃ H H 90–95 3.67 Cl SO₂CH₃ H O C₂H₅ C₂H₅ CH₂ CH₃ H H 70–75 3.68 Cl SO₂CH₃ H O C₂H₅ C₂H₅ CH₂ C₂H₅ H H 50–55 3.69 Cl SO₂CH₃ H O OCH₃ H CH₂ CH₃ H H 3.18–3.99(11H); 5.78(1H); 7.50(1H); 7.81(1H); 8.09(1H). 3.70 Cl SO₂CH₃ H O CH₃ H CHCH₂Cl CH₃ H H 1.52(3H); 3.30–4.12(8H); 4.36(1H); 4.93(1H); 7.49(1H); 7.81(1H); 8.09(1H). 3.71 Cl SO₂CH₃ H O CH₃ H CHCH₂Cl C₂H₅ H H 1.27(3H); 1.55(3H); 3.28–4.02(7H); 4.37(1H); 4.92(1H); 7.48(1H); 7.80(1H); 8.07(1H). 3.72 Cl SO₂CH₃ H C(CH₃)₂ H H O CH₃ H H 132–135 3.73 Cl SO₂CH₃ H O OC₂H₅ H CH₂ CH₃ H H  95–100 3.74 Cl SO₂CH₃ H O OC₂H₅ H CH₂ C₂H₅ H H 1.16(3H); 1.27(3H); 3.20–4.00(9H); 5.89(1H); 7.50(1H); 7.82(1H); 8.07(1H). 3.75 Cl SO₂CH₃ H O C₂H₅ C₂H₅ CH₂ C₂H₅ K⁺ H 200–205 3.76 Cl SO₂C₂H₅ H C(CH₃)₂ H H O CH₃ H H 120–123 3.77 Cl SO₂-n-C₃H₇ H 0 CH₃ CH₃ CH₂ C₂H₅ H H 152–158 3.78 Cl SO₂-n-C₃H₇ H 0 CH₃ CH₃ CH₂ CH₃ H H 172–176 3.79 Cl SO₂-n-C₃H₇ H 0 CH₃ H CH₂ CH₃ H H 188–205 3.80 Cl SCH₃ H O H H CH₂ C₂H₅ H H 1.29(t); 2.56(s); 3.28(t); 3.93(q); 4.49(t); 7.40(s); 7.43(d); 7.55(d). 3.81 Cl SO₂CH₃ H O CH₂Cl H CH₂ C₂H₅ H H 78–82 3.82 CH₃ H H CH₂ H H S C₂H₅ H H 1.44(t); 2.50(s); 3.49(t); 4.09(q); 4.53(t); 7.35(m); 7.48(d); 7.62(d). 3.83 Cl SO₂CH₃ H O CH₂Cl H CH₂ CH₃ H H 81–85 3.84 Cl SCH₃ H O H H CH₂ CH₃ H H 151–153 3.85 Cl SOCH₃ H O H H CH₂ C₂H₅ H H 1.28(t); 2.82(s); 3.40(m); 3.92(m); 4.52(t); 7.45(s); 7.82(d); 8.10(d). 3.86 CH₃ SO₂CH₃ H O H H CH₂ CH₃ H H 205–210 3.87 Cl Cl H CH₂ H H S C₂H₅ H H 173–179 3.88 Cl SCH₃ H CH₂ H H S C₂H₅ H H 1.43(t); 2.51(s); 3.59(t); 4.08(q); 4.51(t); 7.22(d); 7.41(s); 7.50(d). 3.89 Cl SO₂CH₃ H CH₂ H H S C₂H₅ H H 1.50(t); 3.28(s); 3.62(t); 4.10(q); 4.49(t); 7.36(s); 7.68(d); 8.19(d). 3.90 CH₃ SO₂CH₃ H O H H CH₂ C₂H₅ H H 174–180 3.91 Cl SO₂CH₃ H O CH₂Cl H CH₂ CH₃ H H 77–83 3.92 Cl SO₂CH₃ H O F H CH₂ CH₃ H H 3.93 Cl SO₂CH₃ H O F H CH₂ C₂H₅ H H 3.94 Cl SO₂CH₃ H O F F CH₂ CH₃ H H 3.95 Cl SO₂CH₃ H O F F CH₂ C₂H₅ H H 3.96 Cl SO₂CH₃ H O CH₃ H CHCH₃ C₂H₅ H H 183–184 3.97 Cl SO₂CH₃ H O CF₃ H CH₂ CH₃ H H 223–225 3.98 Cl SO₂CH₃ H O CF₃ H CH₂ C₂H₅ H H 183–184 3.99 Cl SO₂CH₃ H O SC₂H₅ H CH₂ CH₃ H H 195–196 3.100 Cl SO₂CH₃ H O SC₂H₅ H CH₂ C₂H₅ H H 199–200 3.101 Cl SO₂CH₃ H O CH₃ H CHCH₃ CH₃ H H 230–233 3.102 Cl SO₂CH₃ H O CHCl(CH₃) H CH₂ C₂H₅ H H 102–107 3.103 Cl SO₂CH₃ H O CHCl(CH₃) H CH₂ CH₃ H H 80–85 3.104 Cl SO₂CH₃ H O n-C₃H₇ H CH₂ CH₃ H H 3.105 Cl SO₂CH₃ H O n-C₃H₇ H CH₂ C₂H₅ H H 3.106 Cl SO₂CH₃ H O H H CH₂ CH₃ ⁺NH₂(CH₃)₂ H 200 3.107 Cl SO₂CH₃ H O H H CH₂ CH₃ ⁺NH₂(CH₂CH₂ H 187 OH) 3.108 Cl SO₂CH₃ H O H H CH₂ CH₃ ⁺NH₃(CH₂CH₂ H 180 OCH₂CH₂OH) 3.109 SCH₃ SCH₃ H O H H CH₂ CH₃ H H 2.33(s); 2.51(s); 3.40(t); 3.70(s); 4.58(t); 5.15(brs); 7.21(s); 7.31(d); 7.42(d). 3.110 SCH₃ SCH₃ H O H H CH₂ C₂H₅ H H 1.38(t); 2.33(s); 2.49(s); 3.41(t); 4.10(q); 4.58(t); 7.25(s); 7.32(d); 7.41(d); 7.82(brs). 3.111 SO₂CH₃ SO₂CH₃ H O H H CH₂ CH₃ H H oil 3.112 SO₂CH₃ SO₂CH₃ H O H H CH₂ C₂H₅ H H oil a) Prepared from 2-chloro-3-(1′-chloro-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoyl chloride with two equivalents of potassium carbonate.

The syntheses of some starting materials are given below:

2-Chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl chloride (compound 4.5)

-   Step a) 2-Chloro-3-methyl-4-methylthioacetophenone     -   A solution of 157 g (2 mol) of acetyl chloride in 420 mol of         1,2-dichlorethane was added dropwise to a suspension of 286 g         (2.14 mol) of aluminum trichloride in 420 ml of         1,2-dichloroethane at 15–20° C. A solution of 346 g (2 mol) of         2-chloro-6-methylthiotoluene in 1 l of 1,2-dichlorethane was         subsequently added dropwise. After the reaction mixture had been         stirred for 12 hours, it was poured into a mixture of 3 l of ice         and 1 l of concentrated HCl. The mixture was extracted with         methylene chloride, and the organic phase was washed with water,         dried with sodium sulfate and concentrated. The residue was         distilled in vacuo. This gave 256 g (60% of theory) of         2-chloro-3-methyl-4-methylthioacetophenone.     -   (m.p.: 46° C.). -   Step b) 2-Chloro-3-methyl-4-methylsulfonylacetophenone     -   163.0 g (0.76 mol) of 2-chloro-3-methyl-4-methylthioacetophenone         were dissolved in 1.5 1 of glacial acetic acid, 18.6 g of sodium         tungstate were added, and 173.3 g of a 30% strength hydrogen         peroxide solution were added dropwise with cooling. Stirring was         continued for 2 days and the mixture was subsequently diluted         with water. The solid which had precipitated was filtered off         with suction, washed with water and dried. This gave 164.0 g         (88% of theory) of         2-chloro-3-methyl-4-methylsulfonylacetophenone.     -   (m.p.: 110–111° C.). -   Step c) 2-Chloro-3-methyl-4-methylsulfonylbenzoic acid     -   82 g (0.33 mol) of         2-chloro-3-methyl-4-methylsulfonylacetophenone were dissolved in         700 ml of dioxane, and 1 l of a 12.5% strength sodium         hypochlorite solution was added at room temperature. Stirring         was continued for 1 hour at 80° C. After cooling, two phases         formed, of which the bottom phase was diluted with water and         acidifed weakly. The solid which had precipitated was filtered         off with suction, washed with water and dried. This gave 60 g         (73% of theory) of 2-chloro-3-methyl-4-methylsulfonylbenzoic         acid.     -   (m.p.: 230–231° C.). -   Step d) Methyl 2-chloro-3-methyl-4-methylsulfonylbenzoate     -   100 g (0.4 mol) of 2-chloro-3-methyl-4-methylsulfonylbenzoic         acid were dissolved in 1 l of methanol and hydrogen chloride gas         was passed in for 5 hours at reflux temperature. The mixture was         subsequently concentrated. This gave 88.5 g (84% of theory) of         methyl 2-chloro-3-methyl-4-methylsulfonylbenzoate.     -   (m.p.: 107–108° C.). -   Step e) Methyl 3-bromomethyl-2-chloro-4-methylsulfonylbenzoate     -   82 g (0.1 mol) of methyl         2-chloro-3-methyl-4-methylsulfonylbenzoate are dissolved in 2 l         of tetrachloromethane, and 56 g (0.31 mol) of N-bromosuccinimide         are added in portions with exposure to light. The reaction         mixture was filtered, the filtrate was concentrated, and the         residue was taken up in 200 ml of methyl tert-butyl ether. The         solution was treated with petroleum ether and the solid which         had precipitated was filtered off with suction and dried. This         gave 74.5 g (70% of theory) of methyl         3-bromomethyl-2-chloro-4-methylsulfonylbenzoate.     -   (m.p.: 74–75° C.). -   Step f) Methyl 2-chloro-3-formyl-4-methylsulfonylbenzoate     -   A solution of 41.0 g (0.12 mol) of methyl         3-bromomethyl-2-chloro-4-methylsulfonylbenzoate in 250 ml of         acetonitrile was treated with 42.1 g (0.36 mol) of         N-methylmorphline N-oxide. The batch was stirred for 12 hours at         room temperature and subsequently concentrated, and the residue         was taken up in ethyl acetate. The solution was extracted with         water, dried with sodium sulfate and concentrated. This gave         31.2 g (94% of theory) of methyl         2-chloro-3-formyl-4-methylsulfonylbenzoate     -   (m.p.: 98–105° C.). -   Step g) 2-Chloro-3-hydroxyiminomethyl-4-methylsulfonylbenzoic acid     -   15.00 g (54 mmol) of methyl         2-chloro-3-formyl-4-methylsulfonylbenzoate and 4,20 g (60 mmol)         of hydroxylamine hydrochloride were taken up in 300 ml of         methanol, and a solution of 3.18 g (30 mmol) of sodium carbonate         in 80 ml of water was added dropwise. After the mixture had been         stirred for 12 hours at room temperature, the methanol was         distilled off, the residue was diluted with water and the         mixture was extracted with diethyl ether. After the organic         phase had been dried, the solvent was removed. This gave 14.40 g         (91% of theory) of methyl         2-chloro-3-hydroxyiminomethyl-4-methylsulfonylbenzoate.     -   (m.p.: 126–128° C.). -   Step h) Methyl     2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate     (compound 4.3)     -   Ethylene was passed for 30 minutes at 15–20° C. into a solution         of 158.0 g (0.54 mol) of methyl         2-chloro-3-hydroxyiminomethyl-4-methylsulfonylbenzoate and 1 l         of dichloromethane. After 1.6 g of sodium acetate had been         added, 454 ml of sodium hypochlorite solution were added         dropwise at 10° C. while simultaneously passing in ethylene.         Ethylene was subsequently passed in at 10° C. for a further 15         minutes. After the mixture had been stirred for 12 hours, the         phases were separated, and the organic phase was washed with         water, dried and concentrated. This gave 156.5 g (90% of theory)         of methyl         2-chloro-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate.     -   (¹H NMR (δ in ppm): 3.24 (s); 3.42 (t); 3.99 (s); 4.60 (t); 7.96         (d); 8.10 (d)). -   Step i)     2-Chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoic acid     (compound 4.4)     -   A solution of 32.8 g of sodium hydroxide, dissolved in 330 ml of         methanol, was slowly added dropwise to a mixture of 170.0 g         (0.54 mol) of methyl         2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate         and 1 l of methanol at 40–45° C. The suspension was stirred for         5 hours at 50° C. After the solvent had been distilled off, the         residue was taken up in 1.5 l of water, and the aqueous phase         was extracted three times with ethyl acetate. The aqueous phase         was acidified with hydrochloric acid and extracted three times         with ethyl acetate. The combined organic phases were         subsequently washed to neutrality with water, dried and         concentrated. This gave 148.8 g (91% of theory) of         2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoic         acid.     -   (¹H NMR (δ in ppm): 3.26 (s); 3.45 (t); 4.63 (t); 8.15 (s); 8.53         (s, br)). -   Step j)     2-Chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl     chloride (compound 4.5)     -   74.8 g (0.63 mol) of thionyl chloride in 50 ml of dry toluene         were added dropwise at 50° C. to a solution of 139.0 g of         2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoic         acid, 1 ml of dimethylformamide and 1 l of dry toluene. After         the mixture had been heated for 6 hours at 110° C., the solvent         was distilled off. This gave 2-chloro-3-(4,5-         dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl chloride in         quantitative yield.     -   (¹H NMR (δ in ppm): 3.25 (s); 3.46 (t); 4.62 (t); 8.21 (dd)).

2-Chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl chloride (compound 4.39)

-   Step a) Methyl     2-chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate     (compound 4.25)     -   Propene was passed for 30 minutes at room temperature into a         solution of 15.0 g (52 mmol) of methyl         2-chloro-3-hydroxyiminomethyl-4-methylsulfonylbenzoate and 200         ml of dichloromethane. After 1.6 g of sodium acetate had been         added, 42.8 ml of sodium hypochlorite solution were added         dropwise at room temperature while simultaneously passing in         propene. Propene was subsequently passed in for a further 15         minutes at room temperature. After the mixture had been refluxed         for 3 hours, it was stirred for 12 hours at room temperature,         propene was again passed in for 5 hours under reflux, and the         mixture was stirred for a further 12 hours at room temperature.         After the phases had been separated, the organic phase was         washed with water, dried and concentrated. This gave 15.5 g (89%         of theory) of methyl         2-chloro-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate.     -   (m.p.: 130–135° C.). -   Step b)     2-Chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoic     acid (compound 4.26)     -   A solution of 3.52 g (88 mmol) of sodium hydroxide, dissolved in         100 ml of methanol, was slowly added dropwise to a mixture of         15.00 g (45 mmol) of methyl         2-chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate         and 200 ml of methanol. The suspension was stirred for 48 hours         at room temperature. After the solvent had been distilled off,         the residue was taken up in water, and the aqueous phase was         washed three times with ethyl acetate. The aqueous phase was         acidified with hydrochloric acid and extracted three times with         ethyl acetate. The combined organic phases were subsequently         washed to neutrality with water, dried and concentrated. This         gave 13.20 g (92% of theory) of         2-chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoic         acid.     -   (m.p.: 173–178° C.). -   Step c)     2-Chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl     chloride (compound 4.39)     -   5.7 g (51 mmol) of thionyl chloride were added dropwise at room         temperture to a solution of 13.0 g (41 mmol) of         2-chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoic         acid, 1 ml of dimethylformamide and 250 ml of dry toluene. The         mixture was subsequently refluxed until the reaction was         complete. After cooling, the solvent was distilled off. This         gave 14.2 g of         2-chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylbenzoyl         chloride in quantitative yield.

2-Chloro-3-(1′-chloro-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoyl chloride

-   Step a) Methyl 2-chloro-3-hydroxycarbonyl-4-methylsulfonylbenzoate     -   13.8 g (0.11 mol) of sodium hydrogen phosphate monohydrate in         170 ml of water, 49.3 g (0.43 mol) of 30% strength hydrogen         peroxide solution and 66.2 g (0.59 mol) of 80% strength aqueous         sodium chlorite solution were added in succession at 5° C. to a         solution of 115.3 g (0.42 mol) of methyl         2-chloro-3-formyl-4-methylsulfonylbenzoate in 2000 ml of         acetonitrile. The reaction solution was subsequently stirred for         1 hour at 5° C. and for 12 hours at room temperature. The pH was         then brought to 1 with 10% strength hydrochloric acid, and 1500         ml of aqueous 40% strength sodium hydrogen sulfite solution were         added. After the mixture had been stirred for 1 hour at room         temperature, the aqueous phase was extracted three times with         ethyl acetate. The combined organic phases were washed with         sodium hydrogen sulfite solution and dried. After the solvent         had been distilled off, 102.0 g of methyl         2-chloro-3-hydroxycarbonyl-4-methylsulfonylbenzoate were         obtained.     -   (¹H NMR (δ in ppm): 3.34 (s); 3.93 (s); 8.08 (s); 14.50 (s,         br.).) -   Step b) Methyl 2-chloro-3-chlorocarbonyl-4-methylsulfonylbenzoate     -   2 drops of dimethylformamide and 11.9 g (0.1 mol) of thionyl         chloride were added to a solution of 6.0 g (0.021 mol) of methyl         2-chloro-3-hydroxycarbonyl-4-methylsulfonylbenzoate and 50 ml of         dry toluene. The solution was refluxed for 4 hours. After the         solvent had been removed in vacuo, 6.2 g of methyl         2-chloro-3-chlorocarbonyl-4-methylsulfonylbenzoate were         obtained.     -   (¹H NMR (δ in ppm): 3.21 (s); 4.02 (s); 8.02 (d); 8.07 (d).) -   Step c) Methyl     2-chloro-3-(1′-hydroxy-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoate     -   A solution of 7.80 g (25 mmol) of methyl         2-chloro-3-chlorocarbonyl-4-methylsulfonylbenzoate was added         dropwise at 0–5° C. to a solution of 4.54 g (50 mmol) of         2,2-dimethylethanolamine in 40 ml of dichloromethane. After the         reaction solution had been stirred for 6 hours at room         temperature, it was extracted three times with water, dried and         concentrated. This gave 8.20 g (80% of theory) of methyl         2-chloro-3-(1′-hydroxy-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoate.     -   (m.p.: 70–72° C.). -   Step d) Methyl     2-chloro-3-(1′-chloro-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoate     -   A mixture of 6.9 g (20 mmol) of methyl         2-chloro-3-(1′-hydroxy-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoate         and 5 ml of thionyl chloride was stirred for 6 hours at room         temperature. The solution was diluted with 50 ml of         dichloromethane and subsequently concentrated. The residue was         dissolved in 20 ml of dichloromethane. The addition of         cyclohexane resulted in a crystalline precipitate which was         filtered off with suction and dried. This gave 6.4 g (88% of         theory) of methyl         2-chloro-3-(1′-chloro-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoate. -   Step e)     2-Chloro-3-(4′,4′-dimethyl-4′,5′-dihydroxazol-2-yl)-4-methylsulfonylbenzoic     acid (compound 4.38)     -   A solution of 5.82 g (15 mmol) of methyl         2-chloro-3-(1′-chloro-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoate         and 0.81 g (20 mmol) of sodium hydroxide in 80 ml of methanol         was stirred for 8 hours at room temperture. After the solvent         had been distilled off, the residue was taken up in water and         the mixture was washed three times with ethyl acetate. The         aqueous phase was acidified with hydrochloric acid and extracted         three times with ethyl acetate. After the organic phase had been         dried, the solvent was removed in vacuo. This gave 3.10 g (56%         of theory) of         2-chloro-3-(4′,4′-dimethyl-4′,5′-dihydrooxazol-2-yl)-4-methylsulfonylbenzoic         acid.     -   (¹H NMR (δ in ppm): 1.34 (s); 3.40 (s); 4.13 (s); 8.07 (s);         13.95 (s, br)). -   Step f)     2-Chloro-3-(1′-chloro-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoyl     chloride     -   A solution of 3.00 g (9 mmol) of         2-chloro-3-(4′,4′-dimethyl-4′,5′-dihydrooxazol-2-yl)-4-methylsulfonylbenzoic         acid, 1.43 g of thionyl chloride and 1 drop of dimethylformamide         in 80 ml of dry toluene was refluxed for 3 hours. After cooling,         the solvent was distilled off in vacuo. This gave 3.43 g (86% of         theory) of         2-chloro-3-(1′-chloro-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoyl         chloride.

Methyl 2-chloro-3-(1,3,4-oxathiazolin-2-on-5-yl)-4-methylsulfonylbenzoate (compound 4.22)

-   Step a) Methyl 3-aminocarbonyl-2-chloro-4-methylsulfonylbenzoate     -   Ammonia was passed for 2 hours into a solution of 15.0 g (48         mmol) of methyl         2-chloro-3-chlorocarbonyl-4-methylsulfonylbenzoate and 300 ml of         dry dioxane. The precipitate formed was filtered off with         suction and the filtrate was concentrated. This gave 15.2 g of         methyl 3-aminocarbonyl-2-chloro-4-methylsulfonylbenzoate in         quantitative yield. -   Step b) Methyl     2-chloro-3-(1,3,4-oxathiazolin-2-on-5-yl)-4-methylsulfonylbenzoate     -   9.80 g (75 mmol) of chlorocarbonylsulfenyl chloride were added         dropwise to a solution of 4.37 g (15 mmol) of methyl         3-aminocarbonyl-2-chloro-4-methylsulfonylbenzoate in 150 ml of         dry toluene. After the mixture had been stirred for 48 hours         under reflux, the solvent was removed in vacuo and the residue         was chromatographed on silica gel (eluent: ethyl         acetate/cyclohexane=1/1). This gave 3.70 g (70% of theory) of         methyl         2-chloro-3-(1,3,4-oxathiazolin-2-on-5-yl)-4-methylsulfonylbenzoate.

Methyl 2-chloro-4-methylsulfonyl-3-(4,5-dihydrooxazol-3-yl)benzoate (compound 4.41)

At room temperature, 41.8 g (0.41 mol) of triethylamine and then 31.1 g (0.10 mol) of methyl 2-chloro-3-chlorocarbonyl-4-methylsulfonylbenzoate in 150 ml of toluene were added dropwise to 26.6 g (0.13 mol) of I-amino-2-bromoethane hydrobromide in 500 ml of toluene. The mixture was heated under reflux for 5 hours and then stirred at room temperature for 12 hours, another 5.0 g (0.02 mol) of I-amino-2-bromoethane hydrobromide were added and the mixture was heated under reflux for 7.5 hours. The reaction mixture was allowed to cool, diluted with ethyl acetate, washed with water, dried and concentrated. The residue was then recrystallized from methyl tert-butyl ether/ethyl acetate. 14.5 g (46% of theory) of methyl 2-chloro-4-methylsulfonyl-3-(4,5-dihydrooxazol-2-yl)benzoate were obtained.

2-Chloro-3-(5-methoxy-5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoic acid (compound 4.60)

-   Step a) Methyl     2-chloro-3-(5-methoxy-5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate     -   7.3 g (102 mmol) of 2-methoxy-1-propene, 28 ml of sodium         hypochlorite solution (12.5% strength) and a spatula-tip of         sodium acetate were added successively to 10.0 g (34 mmol) of         methyl 2-chloro-3-(hydroxyiminomethyl)-4-methylsulfonylbenzoate         in 200 ml of methylene chloride. The mixture was stirred at room         temperature for 12 hours, the solvent was removed and the         residue was taken up in ethyl acetate, washed with water, dried         and concentrated. The residue was chromatographed over silica         gel (eluent: cyclohexane:ethyl acetate=3:2). This gave 5.8 g         (47% of theory) of methyl         2-chloro-3-(5-methoxy-5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate.     -   (mp.: 100–105° C.). -   Step b)     2-Chloro-3-(5-methoxy-5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate     -   At reflux temperature, 5.5 g (15.0 mmol) of methyl         2-chloro-3-(5-methoxy-5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate         in 100 ml of pyridine were added dropwise to 5.0 g (37.5 mmol)         of lithium iodide in 200 ml of pyridine. The mixture was stirred         at this temperature for 4 hours and then cooled, the solvent was         distilled off and the residue was taken up in toluene and         reconcentrated. The residue was subsequently admixed with water         and washed with methylene chloride, and the pH was adjusted to 1         using hydrochloric acid. The aqueous phase was extracted with         methylene chloride and the resulting organic phase was dried and         concentrated. This gave 4.7 g (90% of theory) of         2-chloro-(5-methoxy-5-methyl-4,5-dihydroisoxazol-31-yl)-4-methylsulfonylbenzoate.     -   (mp.: 40–45° C.).

Methyl 2-chloro-3-(2-methyl-2H-1,3,4-dioxazol-5-yl)-4-methylsulfonylbenzoate (compound 4.44)

8.0 g (27.4 mmol) of methyl 2-chloro-3-(hydroxyiminomethyl)-4-methylsulfonylbenzoate in 150 ml of methylene chloride were admixed dropwise with 16.0 g (27.4 mmol) of a 12.5% strength sodium hypochlorite solution, and a spatula-tip of sodium acetate was added. After 1 hour, 34.4 g (0.74 mol) of acetaldehyde were added a little at a time within a period of 36 hours, and the mixture was slowly heated to 55° C. The mixture was subsequently stirred at room temperature for 48 hours, washed with water, dried and concentrated. The residue was then taken up in methylene chloride, 10.0 g (0.23 mol) of acetaldehyde and a spatula-tip of sodium acetate were added and the mixture was heated under reflux for 8 hours. After 72 hours, a further 10.0 g (0.23 mol) of acetaldehyde were added and the mixture was stirred at room temperature. The mixture was subsequently washed with water, dried and concentrated. The residue was passed through silica gel (eluent: isopropanol:cyclohexane=1:9). This gave 5.0 g (55% of theory) of methyl 2-chloro-3-(2-methyl-2H-1,3,4-dioxazol-5-yl)-4-methylsulfonylbenzoate.

Table 4 which follows lists the compounds which have been described above and also further benzoic acid derivatives of the formula III which were prepared, or can be prepared, by a similar method.

TABLE 4

Physical data m.p. [° C.]; No. R¹ R² R³ X R⁴ R⁵ Y R¹⁹ ¹H NMR [δ in ppm] 4.1 Cl Cl H O H H CH₂ OCH₃ 3.29 (t); 3.91 (s); 4.58 (t); 7.46 (d); 7.83 (d). 4.2 Cl Cl H O H H CH₂ OH 3.28 (t); 4.60 (t); 7.02 (s, br); 7.46 (d); 7.98 (a). 4.3 Cl SO₂CH₃ H O H H CH₂ OCH₃ 3.24 (s); 3.42(t); 3.99 (s); 4.60 (t); 7.96 (d); 8.10 (d). 4.4 Cl SO₂CH₃ H O H H CH₂ OH 3.26 (s); 3.45(t); 4.63 (t); 8.15 (s); 8.53 (s, br). 4.5 Cl SO₂CH₃ H O H H CH₂ Cl 3.25 (s); 3.46(t); 4.62 (t); 8.21 (dd). 4.6 Cl Cl H C(CH₃)₂ H H O OH 1.31 (s); 4.16(s); 7.69 (d); 7.90 (d); 13.8 (s, br). 4.7 Cl SO₂C₂H₅ H O CH₃ CH₃ CH₂ OCH₃ 1.25 (t); 1.57 (s); 3.21 (s); 3.42 (q); 3.99 (s); 7.94 (d); 8.07 (d). 4.8 Cl SO₂C₂H₅ H O CH₃ CH₃ CH₂ OH 1.13 (t); 1.47 (s); 3.15 (s); 3.43 (q); 8.06 (s); 13.8 (s, br). 4.9 Cl SO₂C₂H₅ H O H H CH₂ OCH₃ 1.28 (t); 3.41 (m); 4.02 (s); 4.62 (t); 7.95 (d); 8.06 (d). 4.10 Cl SO₂C₂H₅ H O H H CH₂ OH 137–140 4.11 Cl SO₂C₂H₅ H O CH₃ H CH₂ OCH₃ 1.26 (t); 1.53 (d); 3.06 (dd); 3.42 (q); 3.49 (dd); 5.05 (m); 7.95 (d); 8.07 (d). 4.12 Cl SO₂C₂H₅ H O CH₃ H CH₂ OH 140–143 4.13 Cl SO₂CH₃ H CH₂ H H O OCH₃ 3.30 (s); 3.98(s); 4.11 (t); 4.55 (t); 7.97 (d); 8.08 (d). 4.14 Cl SO₂CH₃ H CH₂ H H O OH 3.38 (s); 4.00 (t); 4.46 (t); 8.08 (s). 4.15 Cl SO₂CH₃ H O H H CH₂ OH 3.30 (s); 3.35 (b); 4.15 (s, br); 4.50 (t); 8.05 (s). 4.16 Cl SO₂-n-C₃H₇ H O CH₃ CH₃ CH₂ OCH₃ 0.95 (t); 1.47 (s); 1.58 (quin); 3.12 (s); 3.31 (s); 3.43 (t); 3.93 (s); 8.09 (dd). 4.17 Cl SO₂-n-C₃H₇ H O CH₃ CH₃ CH₂ OH 0.93 (t); 1.47 (s); 1.58 (quin); 3.15 (s); 3.42 (t); 8.05 (s). 4.18 Cl SO₂-n-C₃H₇ H O H H CH₂ OCH₃ 0.92 (t); 1.55 (quin); 3.39 (m); 3.93 (s); 4.50 (t); 8.08 (dd). 4.19 Cl SO₂-n-C₃H₇ H O H H CH₂ OH 148–150 4.20 Cl SO₂-n-C₃H₇ H O CH₃ H CH₂ OCH₃ 0.93 (t); 1.49 (d); 1.58 (quin); 2.94 (dd); 3.42 (m); 3.93 (s); 4.97 (m); 8.10 (dd). 4.21 Cl SO₂-n-C₃H₇ H O CH₃ H CH₂ OH 0.94 (t); 1.39 (d); 1.58 (quin); 2.96 (dd); 3.50 (m); 4.95 (m); 8.05 (s). 4.22 Cl SO₂CH₃ H S ═O O OCH₃ 3.24 (s); 4.02 (s); 8.14 (dd). 4.23 Cl SO₂CH₃ H O COOC₂H₅ H CH₂ OCH₃ 118–121 4.24 Cl SO₂CH₃ H O COOC₂H₅ H CH₂ OH 4.25 Cl SO₂CH₃ H O CH₃ H CH₂ OCH₃ 130–135 4.26 Cl SO₂CH₃ H O CH₃ H CH₂ OH 173–178 4.27 Cl SO₂CH₃ H O CH₃ CH₃ CH₂ OCH₃ 1.57 (s); 3.18 (s); 3.27 (s); 4.01 (s); 7.97 (d); 8.12 (d). 4.28 Cl SO₂CH₃ H O CH₃ CH₃ CH₂ OH 1.48 (s); 3.15 (s); 3.34 (s); 8.08 (dd). 4.29 Cl SO₂CH₃ H O C₂H₅ H CH₂ OCH₃ 0.97 (t); 1.72 (m); 3.10 (dd); 3.32 (s); 3.37 (dd); 4.72 (m); 8.08 (dd). 4.30 Cl SO₂CH₃ H O H —(CH₂)₃—CH— OCH₃ 1.57 (m); 1.81 (m); 2.21 (m); 3.20 (s); 4.02 (s); 4.32 (t); 5.35(dd); 7.92 (d); 8.18 (d). 4.31 Cl SO₂CH₃ H O H —(CH₂)₃—CH— OH 1.72 (m); 2.01 (m); 3.27 (s); 4.24 (t); 5.23 (dd); 8.05 (d); 8.15 (d); 13.8 (s, br). 4.32 Cl SO₂CH₃ H O —(CH₂)₂—O—(CH₂)₂— CH₂ OCH₃ 2.00 (m); 3.23 (s); 3.27 (s), 3.72 (m); 4.00 (s); 7.96 (d); 8.04 (d). 4.33 Cl SO₂CH₃ H O —(CH₂)₂—O—(CH₂)₂— CH₂ OH 78–83 4.34 Cl SO₂CH₃ H O —(CH₂)₄— CH₂ OCH₃ 1.78 (m); 2.24 (m); 3.27 (s); 3.36 (s); 3.98 (s); 7.94 (d); 8.12 (d). 4.35 Cl SO₂CH₃ H O —(CH₂)₄— CH₂ OH 1.76 (m); 2.05 (m); 3.30 (s); 3.33 (s); 8.09 (dd). 4.36 Cl SO₂CH₃ H O C₂H₅ C₂H₅ CH₂ OCH₃ 1.00 (t); 1.85 (m); 3.13 (s); 3.27 (s); 3.98 (s); 7.94 (d); 8.11 (d). 4.37 Cl SO₂CH₃ H O C₂H₅ C₂H₅ CH₂ OH 0.91 (t); 1.76 (m); 3.12 (s); 3.33 (s); 8.07 (dd); 13.75 (s, br). 4.38 Cl SO₂CH₃ H C(CH₃)₂ H H O OH 1.34 (s); 3.40 (s); 4.13 (s); 8.07 (s); 13.95 (s, br). 4.39 Cl SO₂CH₃ H O CH₃ H CH₂ Cl 4.40 Cl SO₂CH₃ H CH₂ H H O OH >260 4.41 Cl SO₂CH₃ H CH₂ H H O OCH₃ 3.29 (3H); 3.96 (3H): 4.12 (2H); 4.55 (2H); 7.98 (1H); 8.09 (1H). 4.42 Cl SCH₃ H O H H CH₂ OCH₃ 202–203 4.43 Cl SO₂CH₃ H O COOMe H CHCO₂CH₃ OCH₃ 1.05 (3H); 1.35 (3H); 3.19 (3H); 4.01 (3H); 4.09 (2H); 4.35 (2H); 5.06 (1H); 5.77 (1H); 8.08 (1H); 8.17 (1H). 4.44 Cl SO₂CH₃ H O CH₃ H O OCH₃ 1.78 (3H); 3.30 (3H); 3.98 (3H); 6.40 (1H); 8.08 (1H); 8.15 (1H). 4.45 Cl SO₂CH₃ H O CHO H CHCH₃ OCH₃ 80–85 4.46 Cl SO₂CH₃ H O CH₃ H CHCH₂Cl OCH₃ 1.65 (3H); 3.27 (3H); 3.50 (2H); 4.00 (3H); 4.22 (1H); 4.88/5.08 (1H); 7.99 (1H); 8.12 (1H). 4.47 Cl SO₂CH₃ H O CH₃ H CHCH₂Cl OH 100–105 4.48 Cl SO₂CH₃ H O CHO H CHCH₃ OH 180–185 4.49 Cl SO₂CH₃ H O SC₂H₅ H CH₂ OCH₃ 1.30 (3H); 2.75 (2H); 3.25 (1H); 3.34 (3H); 3.78 (1H); 3.94 (3H); 6.22 (1H); 8.15 (2H). 4.50 Cl SO₂CH₃ H O SC₂H₅ H CH₂ OH 65–67 4.51 Cl SO₂CH₃ H O CH₃ H CHCH₃ OCH₃ 1.01 (3H); 1.28 (3H); 3.33 (4H); 3.96 (3H); 4.98 (1H); 8.12 (1H); 8.20 (1H). 4.52 Cl SO₂CH₃ H O CH₃ H CHCH₃ OH 68–75 4.53 Cl SO₂CH₃ H O OCOCH₃ H CH₂ OCH₃ 105–110 4.54 Cl SO₂CH₃ H O H H CH₂ OH 4.55 Cl SO₂CH₃ H O OCOCH₃ H CH₂ OH 45–50 4.56 Cl SO₂CH₃ H O OCH₃ H CH₂ OH 60–65 4.57 Cl SO₂CH₃ H O CHCl(CH₃) H CH₂ OCH₃ 1.63 (3H); 3.23 (3H); 3.50 (2H); 3.99 (3H); 4.25 (1H); 4.83/5.03 (1H); 7.96 (1H); 8.13 (1H). 4.58 Cl SO₂CH₃ H O CHCl(CH₃) H CH₂ OH 1.56 (3H); 3.33 (3H); 3.43 (2H); 4.36 (1H); 4.93 (1H); 8.10 (2H). 4.59 Cl SO₂CH₃ H O CH₃ OCH₃ CH₂ OCH₃ 100–105 4.60 Cl SO₂CH₃ H O CH₃ OCH₃ CH₂ OH 40–45 4.61 Cl SO₂CH₃ H O CF₃ OCOCH₃ CH₂ OCH₃ 60–65 4.62 Cl SCH₃ H O H H CH₂ OH 4.63 Cl SO₂Me H O COCH₃ H CH₂ OCH₃ 2.36 (3H); 3.25 (3H); 3.66 (2H); 4.01 (3H); 5.20 (1H); 8.01 (1H); 8.12 (1H). 4.64 Cl SO₂CH₃ H O CF₃ H CH₂ OCH₃ 156 4.65 Cl SO₂CH₃ H O CF₃ H CH₂ OH 170 4.66 Cl SO₂CH₃ H O F F CH₂ OCH₃ 4.67 Cl SO₂CH₃ H O F F CH₂ OH 4.68 Cl SO₂CH₃ H O F H CH₂ OCH₃ 142–143 4.69 Cl SO₂CH₃ H O F H CH₂ OH 4.70 Cl SO₂CH₃ H O CH₂Cl H CH₂ OCH₃ 107–110 4.71 Cl SO₂CH₃ H O CH₂Cl H CH₂ OH 60–65 4.72 Cl SO₂CH₃ H O OCH₃ H CH₂ OCH₃ 105–110 4.73 Cl SO₂CH₃ H O OC₂H₅ H CH₂ OCH₃ 155–160 4.74 Cl SO₂CH₃ H CH₂ H H S OCH₃ 4.75 CH₃ H H C═O H H S OCH₃ 112–120 4.76 Cl SO₂CH₃ H O CF₃ OH CH₂ OH 3.38 (s); 3.56 (d); 3.79 (d); 8.16 (s); 8.67 (s, br). 4.77 Cl SO₂CH₃ H O O-t-C₄H₉ H CH₂ OCH₃ 130–135 4.78 Cl SO₂CH₃ H O O-t-C₄H₉ H CH₂ OH 1.25 (s); 3.05 (dd); 3.34 (s); 3.45 (dd); 6.17 (m); 8.08 (s). 4.79 Cl SO₂CH₃ H O CH₃ H CHCH₃ OCH₃ 1.01 (d); 1.28 (d); 3.35 (m); 3.96 (s); 4.99 (m); 8.12 (d); 8.20 (d). 4.80 Cl SO₂CH₃ H O CH₃ H CHCH₃ OH 68–75 4.81 Cl SO₂CH₃ H O SC₂H₅ H CH₂ OCH₃ 1.30 (t); 2.77 (q); 3.25 (dd); 3.34 (s); 3.78 (dd); 3.94 (s); 6.22 (m), 8.24 (s). 4.82 Cl SO₂CH₃ H O SC₂H₅ H CH₂ OH 65–67 4.83 SCH₃ SCH₃ H O H H CH₂ OCH₂CH₃ 1.28 (t); 2.30 (s); 2.46 (s); 3.28 (t); 4.31 (q); 4.45 (t); 7.42 (d); 7.68 (d). 4.84 SCH₃ SCH₃ H O H H CH₂ OH 2.32 (s); 2.48 (s); 3.28 (t); 4.42 (t); 7.48 (d); 7.64 (d); 13.2 (s). 4.85 SO₂CH₃ SO₂CH₃ H O H H CH₂ OH 3.25 (s); 3.35 (s); 3.44 (t); 8.05 (d); 8.45 (d).

The 3-heterocyclyl-substituted benzoyl derivatives of the formula I and their agriculturally useful salts are suitable as herbicides, both in the form of isomer mixtures and in the form of the pure isomers. The herbicidal compositions comprising compounds of the formula I effect very good control of vegetation on non-crop areas, especially at high rates of application. In crops such as wheat, rice, maize, soybeans and cotton they act against broad-leaved weeds and grass weeds without damaging the crop plants substantially. This effect is observed especially at low rates of application.

Depending on the application method in question, the compounds of the formula I, or herbicidal compositions comprising them, can additionally be employed in a further number of crop plants for eliminating undesirable plants. Examples of suitable crops are the following:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

Moreover, the compounds of the formula I can also be used in crops which tolerate the action of herbicides due to breeding including genetic engineering methods.

The compounds of the formula I, or the herbicidal compositions comprising them, can be employed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also highly-concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend on the intended purposes; in any case, they should guarantee the finest possible distribution of the active ingredients according to the invention.

The herbicidal compositions comprise a herbicidally active amount of at least one compound of the formula I or of an agriculturally useful salt of I and auxiliaries conventionally used for the formulation of crop protection products.

Suitable Inert Auxiliaries are Essentially: mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, eg. amines such as N-methylpyrrolidone and water.

Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agent, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetting agent, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and these concentrates are suitable for dilution with water.

Suitable surfactants (adjuvants) are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, eg. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylaryl sulfonates, of alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ether, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene, or of the naphthalenesulfonic acids, with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl, tributylphenyl olyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.

Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

Granules, eg. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic material, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.

The concentrations of the compounds of the formula I in the ready-to-use products can be varied within wide ranges. In general, the formulations comprise approximately from 0.001 to 98% by weight. preferably 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

The formulation examples below illustrate the preparation of such products:

-   I. 20 parts by weight of the compound No. 3.2 are dissolved in a     mixture composed of 80 parts by weight of alkylated benzene, 10     parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1     mol of oleic acid N-monoethanolamide, 5 parts by weight of calcium     dodecylbenzenesulfonate and 5 parts by weight of the adduct of 40     mol of ethylene oxide and 1 mol of castor oil. Pouring the solution     into 100,000 parts by weight of water and finely distributing it     therein gives an aqueous dispersion which comprises 0.02% by weight     of the active ingredient. -   II. 20 parts by weight of the compound No. 3.9 are dissolved in a     mixture composed of 40 parts by weight of cyclohexanone, 30 parts by     weight of isobutanol, 20 parts by weight of the adduct of 7 mol of     ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of     the adduct of 40 mol of ethylene oxide and 1 mol of castor oil.     Pouring the solution into 100,000 parts by weight of water and     finely distributing it therein gives an aqueous dispersion which     comprises 0.02% by weight of the active ingredient. -   III. 20 parts by weight of the active ingredient No. 3.10 are     dissolved in a mixture composed of 25 parts by weight of     cyclohexanone, 65 parts by weight of a mineral oil fraction of     boiling point 210 to 280° C. and 10 parts by weight of the adduct of     40 mol of ethylene oxide and 1 mol of castor oil. Pouring the     solution into 100,000 parts by weight of water and finely     distributing it therein gives an aqueous dispersion which comprises     0.02% by weight of the active ingredient. -   IV. 20 parts by weight of the active ingredient No. 3.16 are mixed     thoroughly with 3 parts by weight of sodium     diisobutylnaphthalenesulfonate, 17 parts by weight of the sodium     salt of a lignosulfonic acid from a sulfite waste liquor and 60     parts by weight of pulverulent silica gel and the mixture is ground     ina hammer mill. Finely distributing the mixture in 20,000 parts by     weight of water gives a spray mixture which compries 0.1% by weight     of the active ingredient. -   V. 3 parts by weight of the active ingredient No. 3.21 are mixed     with 97 parts by weight of finely divided kaolin. This gives a dust     which comprises 3% by weight of the active ingredient. -   VI. 20 parts by weight of the active ingredient No. 3.22 are mixed     intimately with 2 parts by weight of calcium     dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol     polyglycol ether, 2 parts by weight of the sodium salt of a     phenol/urea/formaldehyde condensate and 68 parts by weight of a     paraffinic mineral oil. This gives a stable oily dispersion. -   VII. 1 part by weight of the active ingredient No. 3.34 is dissolved     in a mixture composed of 70 parts by weight of cyclohexanone, 20     parts by weight of ethoxylated isooctylphenol and 10 parts by weight     of ethoxylated castor oil. This gives a stable emulsion concentrate. -   VIII. 1 part by weight of active ingredient No. 3.35 is dissolved in     a mixture composed of 80 parts by weight of cyclohexanone and 20     parts by weight of Wettol® EM 31 (=nonionic emulsifier based on     ethoxylated castor oil). This gives a stable emulsion concentrate.

The compounds of the formula I, or the herbicidal compositions comprising them, can be applied pre- or post-emergence. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spray apparatus, in such a way that they come into as little contact as possible, if any, with the leaves of the sensitive crop plants while reaching the leaves of undesirable plants which grow underneath, or the bare soil (post-directed, lay-by).

Depending on the intended aim of the control measures, the season, the target plants and the growth stage, the application rates of the compound of the formula I are from 0.001 to 3.0, preferably 0.01 to 1.0 kg/ha of active substanz (a.s.).

To widen the spectrum of action and to achieve synergistic effects, the 3-heterocyclyl-substituted benzoyl derivatives of the formula I can be mixed and applied jointly with a large number of representatives of other groups of herbicidally or growth-regulatory active ingredients. Suitable components in mixtures are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy-/hetaryloxyalkanic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-(hetaroyl/aroyl)-1,3-cyclohexandiones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF₃-phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexenone oxime ether derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofuranes, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and hetaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolcarboxamides and uracils.

Moreover, it may be advantageous to apply the compounds of the formula I, alone or in combination with other herbicides, in the form of a mixture with additional other crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are employed for treating nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.

Use Examples

The herbicidal action of 3-heterocyclyl-substituted benzoyl derivatives of the formula I was demonstrated by the following greenhouse experiments:

The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as substrate. The seeds of the test plants were sown separately for each species.

For the pre-emergence treatment, the active ingredients, suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants had rooted. This cover caused uniform germination of the test plants unless this was adversely affected by the active ingredients.

For the post-emergence treatment, the test plants were grown to a plant height of from 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. To this end, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment. The rate of application for the post-emergence treatment was 31.2 or 15.6 g/ha a.s. (active substance).

Depending on the species, the plants were kept at from 10 to 25° C. and 20 to 35° C., respectively. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.

Evaluation was carried out using a scale of from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial parts, and 0 means no damage or normal course of growth.

The plants used in the greenhouse experiments belonged to the following species:

Scientific name Common name Chenopodium album lambsquarters (goosefoot) Setaria faberii giant foxtail Sinapsis alba white mustard Solanum nigrum black nightshade Triticum aestivum wheat Zea mays Indian corn

Compound 3.33 (Table 3) was very effective against the abovementioned mono- and dicotyledonous harmful plants and was well tolerated in winter wheat and maize when applied post-emergence at rates of application of 31.2 and 15.6 g/ha, respectively. 

1. A 3-heterocyclyl-substituted benzoyl compound of formula I

where the variables have the following meanings: R¹, R² are hydrogen, nitro, halogen, cyano, C₁–C₆-alkyl, C₁–C₆-haloalkyl, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy, C₁–C₆-alkylthio, C₁–C₆-haloalkylthio, C₁–C₆-alkylsulfinyl, C₁–C₆-haloalkylsulfinyl, C₁–C₆-alkylsulfonyl or C₁–C₆-haloalkylsulfonyl; R³ is hydrogen, halogen or C₁–C₆-alkyl; R⁴, R⁵ are hydrogen, halogen, cyano, nitro, C₁–C₄-alkyl, C₁–C₄-alkoxy-C₁–C₄-alkyl, di(C₁–C₄-alkoxy)-C₁–C₄-alkyl, di(C₁–C₄-alkyl)-amino-C₁–C₄-alkyl, [2,2-di(C₁–C₄-alkyl)-1-hydrazino]-C₁–C₄-alkyl, C₁–C₆-alkyliminooxy-C₁–C₄-alkyl, C₁–C₄-alkoxycarbonyl-C₁–C₄-alkyl, C₁–C₄-alkylthio-C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-cyanoalkyl, C₃–C₈-cycloalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy, hydroxyl, C₁–C₄-alkylcarbonyloxy, C₁–C₄-alkylthio, C₁–C₄-haloalkylthio, di(C₁–C₄-alkyl)amino, COR⁶, phenyl or benzyl, it being possible for the two last-mentioned substituents to be fully or partially halogenated and/or to have attached to them one to three of the following groups: nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or C₁–C₄-haloalkoxy; or R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl; or R⁴ and R⁵ together with the corresponding carbon from a carbonyl or thiocarbonyl group; R⁶ is hydrogen, C₁–C₄-alkyl, C₁–C₄-halogalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy, C₃–C₆-alkenyloxy, C₃–C₆-alkynyloxy or NR⁷R⁸; R⁷ is hydrogen or C₁–C₄-alkyl; R⁸ is C₁–C₄-alkyl; X is CR¹⁰R¹¹; Y is O, S, or NR¹²; R⁹, R¹² are hydrogen or C₁–C₄-alkyl; R¹⁰, R¹¹ are hydrogen, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxycarbonyl, C₁–C₄-haloalkoxycarbonyl or CONR⁷R⁸; or R⁴ and R⁹ or R⁴ and R¹⁰ or R⁵ and R¹² together form a C₂–C₆-alkane-diyl chain which can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl; R¹⁵ is a pyrazole of the formula II which is linked in the 4-position

where R¹⁶ is C₁–C₆-alkyl; Z is H or SO₂R¹⁷; R¹⁷ is C₁–C₄-alkyl, C₁–C₄-haloalkyl, phenyl or phenyl which is partially or fully halogenated and/or has attached to it one to three of the following groups: nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or C₁–C₄-haloalkoxy; R¹⁸ is hydrogen or C₁–C₆-alkyl; with the exception of 4-[2-chloro-3-(4,5-dihydrothiazol-2-yl)-4-methylsulfonylbenzoyl]-1,3-di-methyl-5-hydroxy-1H-pyrazol or an agriculturally useful salt thereof.
 2. A 3-heterocyclyl-substituted benzoyl compound of formula I as claims in claim 1, where the variables have the following meanings: R¹, R² are hydrogen, nitro, halogen, cyano, C₁–C₆-alkyl, C₁–C₆-haloalkyl, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy, C₁–C₆-alkylthio, C₁–C₆-haloalkylthio, C₁–C₆-alkylsulfinyl, C₁–C₆-haloalkylsulfinyl, C₁–C₆-alkylsulfonyl or C₁–C₆-haloalkylsulfonyl; R³ is hydrogen, halogen or C₁–C₆-alkyl; R⁴, R⁵ are hydrogen, halogen, cyano, nitro, C₁–C₄-alkyl, C₁–C₄-alkoxy-C₁–C₄-alkyl, di(C₁–C₄-alkoxy)-C₁–C₄-alkyl, di(C₁–C₄-alkyl)-amino-C₁–C₄-alkyl, [2,2-di(C₁–C₄-alkyl)-1-hydrazino]-C₁–C₄-alkyl, C₁–C₆-alkyliminooxy-C₁–C₄-alkyl, C₁–C₄-alkoxycarbonyl-C₁–C₄-alkyl, C₁–C₄-alkylthio-C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-cyanoalkyl, C₃–C₈-cycloalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy, hydroxyl, C₁–C₄-alkylcarbonyloxy, C₁–C₄-alkythio, C₁–C₄-haloalkylthio, di(C₁–C₄-alkyl)amino, COR⁶, phenyl or benzyl, it being possible for the two last-mentioned substituents to be fully or partially halogenated and/or to have attached to them one to three of the following groups: nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or C₁–C₄-haloalkoxy; or R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl; or R⁴ and R⁵ together with the corresponding carbon from a carbonyl or thiocarbonyl group; R⁶ is C₁–C₄-alkyl, C₁–C₄-halogalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy, C₃–C₆-alkenyloxy, C₃–C₆-alkynyloxy or NR⁷R⁸; R⁷ is hydrogen or C₁–C₄-alkyl; R⁸ is C₁–C₄-alkyl; X is CR¹⁰R¹¹; Y is O, S, or NR¹²; R⁹, R¹² are hydrogen or C₁–C₄-alkyl; R¹⁰, R¹¹ are hydrogen, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxycarbonyl, C₁–C₄-haloalkoxycarbonyl or CONR⁷R⁸; or R⁴ and R⁹ or R⁴ and R¹⁰ or R⁵ and R¹² together form a C₂–C₆-alkane-diyl chain which can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl; R¹⁵ is a pyrazole of the formula II which is linked in the 4-position

where R¹⁶ is C₁–C₆-alkyl; Z is H or SO₂R¹⁷; R¹⁷ is C₁–C₄-alkyl, C₁–C₄-haloalkyl, phenyl or phenyl which is partially or fully halogenated and/or has attached to it one to three of the following groups: nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or C₁–C₄-haloalkoxy; R¹⁸ is hydrogen or C₁–C₆-alkyl; with the exception of 4-[2-chloro-3-(4,5-dihydrothiazol-2-yl)-4-methylsulfonylbenzoyl]-1,3-di-methyl-5-hydroxy-1H-pyrazol or an agriculturally useful salt thereof.
 3. A 3-heterocyclyl-substituted benzoyl compound of formula I as claimed in claim 1 or 2, where R³ is hydrogen.
 4. A 3-heterocyclyl-substituted benzoyl compound of formula I as claimed in claim 1 or 2, where R¹, R² are nitro, halogen, cyano, C₁–C₆-alkyl, C₁–C₆-haloalkyl, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy, C₁–C₆-alkylthio, C₁–C₆-haloalkylthio, C₁–C₆-alkylsulfinyl, C₁–C₆-haloalkylsulfinyl, C₁–C₆-alkylsulfonyl or C₁–C₆-haloalkylsulfonyl.
 5. A 3-heterocyclyl-substituted benzoyl compound of formula I as claimed in claim 1 or 2, where R⁴ is halogen, nitro, C₁–C₄-alkyl, C₁–C₄-alkoxy-C₁–C₄-alkyl, C₁–C₄-alkoxycarbonyl-C₁–C₄-alkyl, C₁–C₄-alkylthio-C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-cyanoalkyl, C₃–C₈-cycloalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy, C₁–C₄-alkylthio, C₁–C₄-haloalkylthio, di(C₁–C₄-alkyl)amino, COR⁶, phenyl or benzyl, it being possible for the two last-mentioned substitucnts to be fully or partially halogenated and/or to have attached to them one to three of the following groups: nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or haloalkoxy; R⁵ is hydrogen or C₁–C₄-alkyl; or R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl.
 6. A 3-heterocyclyl-substituted benzoyl compound of formula I as claimed in claim 1 or 2, where R⁴ is C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxycarbonyl or CONR⁷R⁸; R⁵ is hydrogen or C₁–C₄-alkyl; or R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl.
 7. A 3-heterocyclyl-substituted benzoyl compound of formula I as claimed in claim 1 or 2, where R⁴ and R⁵ are hydrogen.
 8. A 3-heterocyclyl-substituted benzoyl compound of formula I as claimed in claim 1 or 2, where R¹⁸ is hydrogen.
 9. A 3-heterocyclyl-substituted benzoyl compound of formula I as claimed in claim 1 or 2, where R⁴ is halogen, nitro, C₁–C₄-alkyl, C₁–C₄-alkoxy-C₁–C₄-alkyl, C₁–C₄-alkoxycarbonyl-C₁–C₄-alkyl, C₁–C₄-alkylthio-C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-cyanoalkyl, C₃–C₈-cycloalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy, C₁–C₄-alkylthio, C₁–C₄-haloalkylthio, di(C₁–C₄-alkyl)amino, COR⁶, phenyl or benzyl, it being possible for the two last-mentioned substituents to be fully or partially halogenated and/or to have attached to them one to three of the following groups: nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or C₁–C₄-haloalkoxy; R⁵ is hydrogen or C₁–C₄-alkyl; or R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl; or R⁴ and R⁹ or R⁴ and R¹⁰ or R⁵ and R¹² together form a C₂–C₆-alkane-diyl chain which can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl.
 10. A composition comprising a herbicidally active amount of at least one 3-heterocyclyl-substituted benzoyl compound of formula I as defined in claim 1 or 2 or of an agriculturally useful salt thereof, and auxiliaries conventionally used for the information of crop protection products.
 11. A 3-heterocyclyl-substituted benzoyl compound of formula

where the variables have the following meanings: R¹, R² are hydrogen, nitro, halogen, cyano, C₁–C₆-alkyl, C₁–C₆-haloalkyl, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy, C₁–C₆-alkylthio, C₁–C₆-haloalkylthio, C₁–C₆-alkylsulfinyl, C₁–C₆-haloalkylsulfinyl, C₁–C₆-alkylsulfonyl or C₁–C₆-haloalkylsulfonyl; R³ is hydrogen, halogen or C₁–C₆-alkyl; R⁴ is halogen, nitro, C₁–C₄-alkyl, C₁–C₄-alkoxy-C₁–C₄-alkyl, C₁–C₄-alkoxycarbonyl-C₁–C₄-alkyl, C₁–C₄-alkylthio-C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-cyanoalkyl, C₃–C₈-cycloalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy, C₁–C₄-alkylthio, C₁–C₄-haloalkylthio, di(C₁–C₄-alkyl)amino, COR⁶, phenyl or benzyl, it being possible for the two last-mentioned substituents to be fully or partially halogenated and/or to have attached to them one to three of the following groups: nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or C₁–C₄-haloalkoxy; R⁵ is hydrogen or C₁–C₄-alkyl; or R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl; R⁶ is hydrogen, C₁–C₄-alkyl, C₁–C₄-halogalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy, C₃–C₆-alkenyloxy, C₃–C₆-alkynyloxy or NR⁷R⁸; R⁷ is hydrogen or C₁–C₄-alkyl; R⁸ is C₁–C₄-alkyl; X is CR¹⁰R¹¹; Y is O, or S, NR¹²; R⁹, R¹² are hydrogen or C₁–C₄-alkyl; R¹⁰, R¹¹ are hydrogen, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxycarbonyl, C₁–C₄-haloalkoxycarbonyl or CONR⁷R⁸; or R¹⁵ is a pyrazole of the formula II which is linked in the 4-position

where R¹⁶ is C₁–C₆-alkyl; Z is H; R¹⁷ is C₁–C₄-alkyl, C₁–C₄-haloalkyl, phenyl or phenyl which is partially or fully halogenated and/or has attached to it one to three of the following groups: nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or C₁–C₄-haloalkoxy; R¹⁸ is hydrogen or C₁–C₆-alkyl; where X and Y are not simultaneously sulfur; or an agriculturally useful salt thereof.
 12. A 3-heterocyclyl-substituted benzoyl compound of formula I as claimed in claim 11 where the variables have the following meanings: R¹, R² are hydrogen, nitro, halogen, cyano, C₁–C₆-alkyl, C₁–C₆-haloalkyl, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy, C₁–C₆-alkylthio, C₁–C₆-haloalkylthio, C₁–C₆-alkylsulfinyl, C₁–C₆-haloalkylsulfinyl, C₁–C₆-alkylsulfonyl or C₁–C₆-haloalkylsulfonyl; R³ is hydrogen, halogen or C₁–C₆-alkyl; R⁴ is halogen, nitro, C₁–C₄-alkyl, C₁–C₄-alkoxy-C₁–C₄-alkyl, C₁–C₄-alkoxycarbonyl-C₁–C₄-alkyl, C₁–C₄-alkylthio-C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-cyanoalkyl, C₃–C₈-cycloalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy, C₁–C₄-alkylthio, C₁–C₄-haloalkylthio, di(C₁–C₄-alkyl)amino, COR⁶, phenyl or benzyl, it being possible for the two last-mentioned substituents to be fully or partially halogenated and/or to have attached to them one to three of the following groups: nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or C₁–C₄-haloalkoxy; R⁵ is hydrogen or C₁–C₄-alkyl; or R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl; R⁶ is C₁–C₄-alkyl, C₁–C₄-halogalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy, C₃–C₆-alkenyloxy, C₃–C₆-alkynyloxy or NR⁷R⁸; R⁷ is hydrogen or C₁–C₄-alkyl; R⁸ is C₁–C₄-alkyl; X is CR¹⁰R¹¹; Y is O, S, or NR¹²; R⁹, R¹² are hydrogen or C₁–C₄-alkyl; R¹⁰, R¹¹ are hydrogen, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxycarbonyl, C₁–C₄-haloalkoxycarbonyl or CONR⁷R⁸; or R¹⁵ is a pyrazole of the formula II which is linked in the 4-position

where R¹⁶ is C₁–C₆-alkyl; Z is H; R¹⁷ is C₁–C₄-alkyl, C₁–C₄-haloalkyl, phenyl or phenyl which is partially or fully halogenated and/or has attached to it one to three of the following groups: nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or C₁–C₄-haloalkoxy; R¹⁸ is hydrogen or C₁–C₆-alkyl; where X and Y are not simultaneously sulfur; or an agriculturally useful salt thereof.
 13. A 3-heterocyclyl-substituted benzoyl compound of formula I as claimed in claim 11, where R³ is hydrogen.
 14. A 3-heterocyclyl-substituted benzoyl compound of formula I as claimed in claim 11, where R¹, R² are nitro, halogen, cyano, C₁–C₆-alkyl, C₁–C₆-haloalkyl, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy, C₁–C₆-alkylthio, C₁–C₆-haloalkylthio, C₁–C₆-alkylsulfinyl, C₁–C₆-haloalkylsulfinyl, C₁–C₆-alkylsulfonyl or C₁–C₆-haloalkylsulfonyl.
 15. A 3-heterocyclyl-substituted benzoyl compound of formula I as claimed in claim 11, where R⁴ is C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxycarbonyl or CONR⁷R⁸; R⁵ is hydrogen or C₁–C₄-alkyl; or R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl.
 16. A 3-heterocyclyl-substituted benzoyl compound of formula I as claimed in claim 11, where R¹⁸ is hydrogen.
 17. A 3-heterocyclyl-substituted benzoyl compound of formula I as claimed in claim 11, where R⁴ is halogen, nitro, C₁–C₄-alkyl, C₁–C₄-alkoxy-C₁–C₄-alkyl, C₁–C₄-alkoxycarbonyl-C₁–C₄-alkyl, C₁–C₄-alkylthio-C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-cyanoalkyl, C₃–C₈-cycloalkyl, C₁–C₄-alkoxy, C₁–C₄-alkoxy-C₂–C₄-alkoxy, C₁–C₄-haloalkoxy, C₁–C₄-alkylthio, C₁–C₄-haloalkylthio, di(C₁–C₄-alkyl)amino, COR⁶, phenyl or benzyl, it being possible for the two last-mentioned substituents to be fully or partially halogenated and/or to have attached to them one to three of the following groups: nitro, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy or C₁–C₄-haloalkoxy; R⁵ is hydrogen or C₁–C₄-alkyl; or R⁴ and R⁵ together form a C₂–C₆-alkanediyl chain which can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl; or R⁴ and R⁹ or R⁴ and R¹⁰ or R⁵ and R¹² together form a C₂–C₆-alkane-diyl chain which can be mono- to tetrasubstituted by C₁–C₄-alkyl and/or interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C₁–C₄-alkyl.
 18. A composition comprising a herbicidally active amount of at least one 3-heterocyclyl-substituted benzoyl compound of formula I as defined in claim 11 or 12 or of an agriculturally useful salt thereof, and auxiliaries conventionally used for the information of crop protection products.
 19. A 3-heterocyclyl-substituted benzoyl derivative of the formula I as claimed in claim 2, where Z is SO₂R¹⁷.
 20. A 3-heterocyclyl-substituted benzoyl derivative of the formula I as claimed in claim 2, where Z is hydrogen. 